28 resultados para DISULFIDE BONDS

em Brock University, Canada


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The study examines the buddy film genre and the representation of masculinity in relation to the homosocial and the homoerotic. As a genre, the buddy films focus on male relationships, thematically seeking to mediate the boundaries surrounding the homosocial continuum and the intimacy and eroticism implicit in male bonding. Theories of genre, gender and identity are used to analyze the construction of masculine identity within the films. By providing a qualitative analysis of films from the 1960s to contemporary times, the research establishes a relationship between social changes, attitudes toward men and depictions of men. The buddy films adapt to address changes in the representation of masculinity, embodied in the difference between the male couple in the films. The early films of the 1960s served as templates that deconstructed traditional representations of male identity through articulating the tension within homosocial relationships. However, in the later films this tension became a refle~ive convention, acting to undermine the eroticism onto a displaced Other. The buddy film genre highlights the tension inherent to the male masquerade. This tension is situated in the need to represent the protagonist's homosocial relationship, while disavowing the eroticism that surrounds homosocial bonding. The structure of the buddy film genre, which focuses on the exploration of masculinity and representing the bonds of homosocial intimacy, makes these films a significant site for investigating the cultural construction of masculine identities.

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In 2007, Barry Bonds hit his 75 6th home run, breaking Hank Aaron's all-time record for most home runs in a Major League career. While it would be expected that such an accomplishment would induce unending praise and adulationfor the new record-holder, Bonds did not receive the treatment typically reserved for a beloved baseball hero. The purpose of this thesis is to assess media representations of the 2007 home run chase in order to shed light upon the factors which led to the mixed representations which accompanied BOlTds ' assault on Aaron's record. Drawingfrom Roland Barthes ' concept of myth, this thesis proposes that Bonds was portrayed in predominantly negative ways because he was seen as failing to embody the values of baseball's mythology. Using a qualitative content analysis of three major American newspapers, this thesis examines portrayals of Bonds and how he was shown both to represent and oppose elements from baseball's mythology, such as youth, and a distant, agrarian past. Recognizing the ways in which baseball is associated with American life, the media representations of Bonds are also evaluated to discern whether he was portrayed as personifYing a distinctly American set of values. The results indicate that, in media coverage of the 2007 home run chase, Bonds was depicted as a player of many contradictions. Most commonly, Bonds' athletic ability and career achievements were contrasted with unflattering descriptions of his character, including discussions of his alleged use of performance-enhancing substances. However, some coverage portrayed Bonds as embodying baseball myth. The findings contribute to an appreciation of the importance of historical context in examining media representations. This understanding is enhanced by an analysis of a selection of articles on Mark McGwire 's record-breaking season in 1998, and careful consideration of, and comparison to, the context under which Bonds performed in 2007. Findings are also shown to support the contemporary existence of a strong American baseball mythology. That Bonds is both condemned for failing to uphold the mythology and praised for personifYing it suggests that the values seen as inherent to baseball continue to act as an American cultural benchmark.

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For the past 20 years, researchers have applied the Kalman filter to the modeling and forecasting the term structure of interest rates. Despite its impressive performance in in-sample fitting yield curves, little research has focused on the out-of-sample forecast of yield curves using the Kalman filter. The goal of this thesis is to develop a unified dynamic model based on Diebold and Li (2006) and Nelson and Siegel’s (1987) three-factor model, and estimate this dynamic model using the Kalman filter. We compare both in-sample and out-of-sample performance of our dynamic methods with various other models in the literature. We find that our dynamic model dominates existing models in medium- and long-horizon yield curve predictions. However, the dynamic model should be used with caution when forecasting short maturity yields

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Glutaredoxins are oxidoreductases capable of reducing protein disulfide bridges and glutathione mixed disulfides through the process of deglutathionylation and glutathionylation. Lately, redox-mediated modifications of functional cysteine residues of TGA1 and TGA8 transcription factors have been postulated. Namely, GRX480 and ROXY1 glutaredoxins have been previously shown to interact with TGA proteins and have been suggested to regulate redox state of these proteins. TGA1, together with TGA2, is involved in systemic acquired resistance (SAR) establishment in the plant Arabidopsis thaliana through PR1 (Pathogenesis related 1) gene activation. They both form an enhanceosome complex with the NPR1 protein (non-expressor of pathogenesis related gene 1) which leads to PR1 transcription. Although TGA1 is capable of activating PR1 transcription, the ability of the TGA1 NPR1 enhanceosome complex to assembly is based on the redox status of TGA1. We identified GRX480 as a glutathionylating enzyme that catalyzes the TGA1 glutathione disulfide transferase reaction with a Km of around 20μM GSSG (oxidized glutathione). Out of four cysteine residues found within TGA1, C172 and C266 were found to be glutathionylated by this enzyme. We also confirmed TGA1 glutathionylation in vivo and showed that this modification takes place while TGA1 is associated with the PR1 promoter enzymatically via GRX480. Furthermore, we show that glutathionylation via GRX480 abolishes TGA1's interaction with NPR1 and consequently prevents the TGA1-NPR1 transcription activation of PR1. When glutathionylated, TGA1 is recruited to the PR1 promoter and acts as a repressor. Therefore, glutathionylation is a mechanism that prevents TGA1 NPR1 interaction, allowing TGA1 to function as a repressor of PR1 transcription. Surprisingly, GRX480 was not able to deglutathionylate proteins demonstrating the irreversible nature of the reaction. Moreover, we demonstrate that other members of CC-class glutaredoxins, namely ROXY1 and ROXY2, can also catalyze protein glutathionylation. The TGA8 protein was previously shown to interact with NPR1 analogs, BOP1 and BOP2 proteins. However, unlike the case of TGA1 NPR1 interaction, here we demonstrate that TGA8-BOP1 interaction is not redox regulated and that TGA8 glutathionylation by ROXY1 and ROXY2 enzymes does not abolish this interaction in vitro. However, TGA8 glutathionylation results in TGA8 oligomer disassembly into smaller complexes and monomers. Our results suggest that CC-Grxs are unable to reduce mixed disulfides, instead they efficiently catalyze the opposite reaction which distinguishes them from traditional glutaredoxins. Therefore, they should not be classified as glutaredoxins but as protein glutathione disulfide transferases.

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Form letter: a printed, 2 1/2 page copy of Jarvis Conklin and Co. Mortgage, Loans and Municipal Bonds letter to S.D. Woodruff, signed by James Conklin, n.d.

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Printed blank to S.D. Woodruff from Jarvis, Conklin and Co. regarding enclosure of coupons for bonds, Jan. 24, 1885.

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Printed blank of Statement of Security Form naming the bond as Jones County Texas Bonds for the purpose of building a courthouse. It is made out to S.D. Woodruff and dated June 12, 1885. An envelope addressed to Mr. S.D. Woodruff is also included. The postmarks are Kansas, 1885 and St. Catharines, June 13, 1885.

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Notice regarding bonds and shareholders and the rights of the directors of the Long Point Company, n.d.

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Flyer (2 double sided pages, printed) about the Dominion Power and Transmission Company bonds from R.W. Harris and Co. Bankers, New York, n.d.

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Flyer (2 double sided pages, printed) about railroad bonds from E.D. Shepard and Co. Bankers, New York, n.d.

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In the work reported here, optically clear, ultrathin TEOS derived sol-gel slides which were suitable for studies of tryptophan (Trp) fluorescence from entrapped proteins were prepared by the sol-gel technique and characterized. The monitoring of intrinsic protein fluorescence provided information about the structure and environment of the entrapped protein, and about the kinetics of the interaction between the entrapped protein and extemal reagents. Initial studies concentrated on the single Trp protein monellin which was entrapped into the sol-gel matrices. Two types of sol-gel slides, termed "wet aged", in which the gels were aged in buffer and "dry-aged", in which the gels were aged in air , were studied in order to compare the effect of the sol-gel matrix on the structure of the protein at different aging stages. Fluorescence results suggested that the mobility of solvent inside the slides was substantially reduced. The interaction of the entrapped protein with both neutral and charged species was examined and indicated response times on the order of minutes. In the case of the neutral species the kinetics were diffusion limited in solution, but were best described by a sum of first order rate constants when the reactions occurred in the glass matrix. For charged species, interactions between the analytes and the negatively charged glass matrix caused the reaction kinetics to become complex, with the overall reaction rate depending on both the type of aging and the charge on the analyte. The stability and conformational flexibility of the entrapped monellin were also studied. These studies indicated that the encapsulation of monellin into dry-aged monoliths caused the thermal unfolding transition to broaden and shift upward by 14°C, and causedthe long-term stability to improve by 12-fold (compared to solution). Chemical stability studies also showed a broader transition for the unfolding of the protein in dry-aged monoliths, and suggested that the protein was present in a distribution of environments. Results indicated that the entrapped proteins had a smaller range of conformational motions compared to proteins in solution, and that entrapped proteins were not able to unfold completely. The restriction of conformational motion, along with the increased structural order of the internal environment of the gels, likely resulted in the improvements in themial and long-term stability that were observed. A second protein which was also studied in this work is the metal binding protein rat oncomodulin. Initially, the unfolding behavior of this protein in aqueous solution was examined. Several single tryptophan mutants of the metal-binding protein rat oncomodulin (OM) were examined; F102W, Y57W, Y65W and the engineered protein CDOM33 which had all 12 residues of the CD loop replaced with a higher affinity binding loop. Both the thermal and the chemical stability were improved upon binding of metal ions with the order apo < Ca^^ < Tb^"^. During thermal denaturation, the transition midpoints (Tun) of Y65W appeared to be the lowest, followed by Y57W and F102W. The placement of the Trp residue in the F-helix in F102W apparently made the protein slightly more thermostable, although the fluorescence response was readily affected by chemical denaturants, which probably acted through the disruption of hydrogen bonds at the Cterminal end of the F-helix. Under both thermal and chemical denaturation, the engineered protein showed the highest stability. This indicated that increasing the number of metal ligating oxygens in the binding site, either by using a metal ion with a higher coordinatenumber (i.e. Tb^*) which binds more carboxylate ligands, or by providing more ligating groups, as in the CDOM33 replacement, produces notable improvements in protein stability. Y57W and CE)OM33 OM were chosen for further studies when encapsulated into sol-gel derived matrices. The kinetics of interaction of terbium with the entrapped proteins, the ability of the entrapped protein to binding terbium, as well as thermal stability of these two entrapped protein were compared with different levels of Ca^"*^ present in the matrix and in solution. Results suggested that for both of the proteins, the response time and the ability to bind terbium could be adjusted by adding excess calcium to the matrix before gelation. However, the less stable protein Y57W only retained at most 45% of its binding ability in solution while the more stable protein CDOM33 was able to retain 100% binding ability. Themially induced denaturation also suggested that CDOM33 showed similar stability to the protein in solution while Y57W was destabilized. All these results suggested that "hard" proteins (i.e. very stable) can easily survive the sol-gel encapsulation process, but "soft" proteins with lower thermodynamic stability may not be able to withstand the sol-gel process. However, it is possible to control many parameters in order to successfully entrap biological molecules into the sol-gel matrices with maxunum retention of activity.

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The main purpose of this thesis is to study properties of La2/3Cai/3Mn03, both polycrystalline ceramics and thin films. This material has striking related electrical and magnetic properties. Thin films show colossal negative magnetoresistance (CMR) near transition from an insulating to a metallic state accompanied closely by transition from a paramagnetic to a ferromagnetic state. The double exchange mechanism (DE) and the Jahn-Teller deformations play an important role in CMR effect. Applied pressure has a very similar effect as does an applied magnetic field, except, at low temperatures (Tbonds in applied pressure axe discussed. The fabrication of La2/3Cai/3Mn03 thin films by pulsed laser deposition was successfully developed. The films grown on (100) SrTiOs substrate are c-axis oriented and exhibit negative magnetoresistance Ap/p(H) of over 400% at 245°C and 4200% at 90 K.

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The phenomenon of communitas has been described as a moment 'in and out of time' in which a collective of individuals may be experienced by one as equal and individuated in an environment stripped of structural attributes (Turner, 1 969). In these moments, emotional bonds form and an experience of perceived 'oneness' and synergy may be described. As a result of the perceived value of these experiences, it has been suggested by Sharpe (2005) that more clearly understanding how this phenomenon may be purposefully facilitated would be beneficial for leisure service providers. Consequently, the purpose of this research endeavor was to examine the ways in which a particular leisure service provider systematically employs specific methods and sets specific parameters with the intention of guiding participants toward experiences associated with communitas or "shared spirit" as described by the organization. A qualitative case study taking a phenomenological approach was employed in order to capture the depth and complexity of both the phenomenon and the purposefiil negotiation of experiences in guiding participants toward this phenomenon. The means through which these experiences were intentionally facilitated was recreational music making in a group drumming context. As such, an organization which employs specific methods of rhythm circle facilitation as well as trains other facilitators all over the world was chosen purposely for their recognition as the most respectable and credible in this field. The specific facilitator was chosen based on high recommendation by the organization due to her level of experience and expertise. Two rhythm circles were held, and participants were chosen randomly by the facilitator. Data was collected through observation in the first circle and participant- observation in the second, as well as through focus groups with circle participants. Interviews with the facilitator were held both initially to gain broad understanding of concepts and phenomenon as well as after each circle to reflect on each circle specifically. Data was read repeatedly to drawn out patterns which emerged and were coded and organized accordingly. It was found that this specific process or system of implementation lead to experiences associated with communitas by participants. In order to more clearly understand this process and the ways in which experiences associated with communitas manifest as a result of deliberate facilitator actions, these objective facilitator actions were plotted along a continuum relating to subjective participant experiences. These findings were then linked to the literature with regards to specific characteristics of communitas. In so doing, the intentional manifestation of these experiences may be more clearly understood for ftiture facilitators in many contexts. Beyond this, findings summarized important considerations with regards to specific technical and communication competencies which were found to be essential to fostering these experiences for participants within each group. Findings surrounding the maintenance of a fluid negotiation of certain transition points within a group rhythm event overall were also highlighted, and this fluidity was found to be essential to the experience of absorption and engagement in the activity and experience. Emergent themes of structure, control, and consciousness have been presented as they manifested and were found to affect experiences within this study. Discussions surrounding the ethics and authenticity of these particular methods and their implementation has also been generated throughout. In conclusion, there was a breadth as well as depth of knowledge found in unpacking this complex process of guiding individuals toward experiences associated with communitas. The implications of these findings contribute in broadening the current theoretical as well as practical understanding as to how certain intentional parameters may be set and methods employed which may lead to experiences of communitas, and as well contribute a greater knowledge to conceptualizing the manifestation of these experiences when broken down.

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A fluorescence excitation spectrum of formic acid monomer (HCOOH) , has been recorded in the 278-246 nm region and has been attributed to an n >7r* electron promotion in the anti conformer. The S^< S^ electronic origins of the HCOOH/HCOOD/DCOOH/DCOOD isotopomers were assigned to weak bands observed at 37431.5/37461.5/37445.5/37479.3 cm'''. From a band contour analysis of the 0°^ band of HCOOH, the rotational constants for the excited state were estimated: A'=1.8619, B'=0.4073, and C'=0.3730 cm'\ Four vibrational modes, 1/3(0=0), j/^(0-C=0) , J/g(C-H^^^) and i/,(0-H^yJ were observed in the spectrum. The activity of the antisymmetric aldehyde wagging and hydroxyl torsional modes in forming progressions is central to the analysis, leading to the conclusion that the two hydrogens are distorted from the molecular plane, 0-C=0, in the upper S. state. Ab initio calculations were performed at the 6-3 IG* SCF level using the Gaussian 86 system of programs to aid in the vibrational assignments. The computations show that the potential surface which describes the low frequency OH torsion (twisting motion) and the CH wagging (molecular inversion) motions is complex in the S^ excited electronic state. The OH and CH bonds were calculated to be twisted with respect to the 0-C=0 molecular frame by 63.66 and 4 5.76 degrees, respectively. The calculations predicted the existence of the second (syn) rotamer which is 338 cm'^ above the equilibrium configuration with OH and CH angles displaced from the plane by 47.91 and 41.32 degrees.

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Therllloelynalllics of lllodel 11lel1ll)rane systeills containing 1110nollnsaturatecl I)lloSI)holil) ids is strongly infllienced l)y the I)osition of the C==C dOlll)le })ond in tIle acyl chain. The telllI)eratllres of both chain-nlelting (TM) and La -+ HI! (TH) I)hase traIlsitions are lowered by IIp to 20°C when C==C is Inoved froln positions 6 or 11 to I)osition 9 in an 18-carl)on chain. This work is an attellll)t to ellicidate the uIlderlying Illoleclilar Illechanisllls reSI)Onsi])le for tllese draillatic tllerillodynaillic changes. Mixtllres of di-18: 1 l)hoSI)hatidylethanolanline with C==C at l)ositioIlS 6, 9, 11 were llsed, witll a sI1lall aI1lOlint of I)erdellterated tetradecanol, known to })e a gooel rel)Orter of the cllain Illoleclilar order. SI)ectral second 11I0I1lents were llsed to Illonitor tIle La -+ HII I)hase transition, which was fOllnd to ])e ])road (2-6°C), with a slight llysteresis on heatiIlg/cooling. The orientational order I)rofiles were nleasllred 1lSiIlg 2H Illiclear Illagnetic resonance and changes in these order I)rofiles between La aIld HII I)hases silow l)oth a local increase in order in the vicinity of the C==C bonds and an o\Terall decrease ill the average orientational order of the chain as a whole. These Sll])tle changes recluire })oth high-fidelity SI)ectrosCol)y and a careflll data analysis that takes into aCCOllnt the effects due to l)artiall1lagnetically-indllced orientational ordering of the l)ilayers. In tIle COIltext of SOllle recently rel)Orted cross-relaxation 11leaSlirenlents in Silllilar l)llOSI)llolil)iels, 0111' reslilts sllggest that large-anll)litllde conforlllational changes in the interior of tIle I110del 111eI11])ranes I)lay a 1110re significant role than I)reviollsly thOllght.