Thesis (M.S.)--Massachusetts Institute of Technology, Alfred P. Sloan School of Management, 1981. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND DEWEY. / Bibliography: leaves 129-133. / by Robert Charles Salipante. / M.S.

Este trabalho tem como objetivo contribuir para o entendimento da interação entre duas substâncias de natureza hidrofílica água e celulose cujas propriedades são fortemente influenciadas pelas pontes ou ligações de hidrogênio. As ligações de hidrogênio, LH, estão presentes nas fibras de celulose reforçando tanto o interior da cadeia polimérica como proporcionando alta aderência entre essas cadeias. A existência de efeitos cooperativos entre essas LH tem sido considerada por alguns autores como um fator que contribui para a grande estabilidade mecânica das fibras de celulose. As propriedades da água são únicas entre os líquidos de baixo peso molecular: alto ponto de ebulição, menor densidade em fase sólida do que em fase líquida, existência de uma fase líquida metaestável água super-resfriada abaixo de 0ºC, etc. Em espaços restritos de natureza hidrofílica a água confinada se comporta de forma análoga a água super-resfriada e atua como um excelente adesivo. O entendimento de sistemas envolvendo materiais hidrofílicos tais como sólidos, géis e macromoléculas e a água, contribui para o desenvolvimento de novos materiais e para o entendimento dos sistemas vivos. Neste trabalho são abordados a adesão entre água e fibras de celulose de diferentes comprimentos e o efeito de determinados íons sobre a viscosidade de suspensões de celulose em água. Os resultados obtidos com celulose de fibras curtas e finas evidenciam a presença de água confinada, através da transição característica da mesma observada em -45ºC(228K). Esta evidência é corroborada pela ausência dessa transição quando os sais, que quebram as LHs e impedem o confinamento da água, estão presentes no sistema formado pela celulose e a água. / This dissertation aims to contribute to understand the interaction between two hydrophilic substances water and cellulose whose properties are strongly influenced by hydrogen bonding. Hydrogen bonds, HB, are present in cellulose fibers reinforcing the interior of the polymeric chain and allowing for high adherence among these chains. These intra and inter HB has been considered by some authors as a factor that contributes to the high mechanical stability of cellulose fibers. The water properties are unique among liquids with low molecular weight: high boiling point, lower density in the solid state phase than in the liquid phase and even at temperatures above 273K, water does not behave as a liquid in restricted space. If confined by two surfaces, the confined water behaves as an excellent adhesive. The understanding of systems involving hydrophilic materials, such as solids, gels, macromolecules, and water contributes to both the development of new materials and the understanding of live systems. This dissertation is a contribution to the understanding of the interaction among cellulose fibers and water. The results obtained with short and fine cellulose fibers show the presence of confined water exhibiting its characteristic transition in -45 º C (228K). This evidence is corroborated by the absence of this transition when the salts which breaks the LHs and thus, prevent the formation of confined water are present in the system formed by the cellulose and water.

Lau Cheuk Man. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2005. / Includes bibliographical references (leaves 93-98). / Abstracts in English and Chinese. / Table of Contents --- p.i / Acknowledgements --- p.iii / Abbreviations --- p.iv / Structural Abbreviations for Porphyrin Complexes --- p.v / Abstract --- p.vi / Chapter Chapter 1 --- Introduction / Chapter 1.1 --- General Introduction --- p.1 / Chapter 1.2 --- Activation of Carbon-Hydrogen Bond (CHA) by Transition Metal --- p.2 / Chapter 1.2.1 --- Application of CHA by Transition Metals --- p.3 / Chapter 1.2.2 --- Thermodynamic in CHA by Transition Metals --- p.5 / Chapter 1.2.3 --- Types of Carbon-Hydrogen Activations --- p.6 / Chapter 1.3 --- Carbon-Hydrogen Bond Activation of Aldehydes --- p.14 / Chapter 1.3.1 --- Catalytic Application of CHA of Aldehydes by Transition Metals --- p.14 / Chapter 1.3.2 --- Stability of Intermediate M(COR) --- p.15 / Chapter 1.3.3 --- Issue in Selectivity --- p.16 / Chapter 1.4 --- Structural Features of Rhodium Porphyrins --- p.23 / Chapter 1.5 --- Objective of the work --- p.24 / Chapter Chapter 2 --- Carbon-Hydrogen Activation of Aldehydes by Rh(ttp)Cl and Rh(ttp)Me / Chapter 2.1 --- Introduction --- p.26 / Chapter 2.2 --- CHA of Aldehydes by Rh(ttp)Cl --- p.27 / Chapter 2.2.1 --- Preparation of Rh(ttp)Cl --- p.27 / Chapter 2.2.2 --- Solvents Screening --- p.27 / Chapter 2.2.3 --- Results and Discussion --- p.30 / Chapter 2.3 --- CHA of Aldehydes by Rh(ttp)Me --- p.33 / Chapter 2.3.1 --- Preparation of Rh(ttp)Me --- p.34 / Chapter 2.3.2 --- Results and Discussion --- p.35 / Chapter 2.4 --- Mechanistic Studies --- p.37 / Chapter 2.4.1 --- CHA of Aldehydes by Rh(ttp)Cl --- p.37 / Chapter 2.4.2 --- CHA of Aldehydes by Rh(ttp)R --- p.42 / Chapter 2.5 --- Comparison of the u(C=0) --- p.48 / Chapter 2.6 --- X-ray Data --- p.49 / Chapter 2.7 --- Summary --- p.50 / Chapter Chapter 3 --- CHA of Aldehydes by Rh(ttp)CH2CH2OH and Rh(ttp)+X- / Chapter 3.1 --- Introduction --- p.52 / Chapter 3.2 --- CHA of Aldehydes by Rh(ttp)CH2CH2OH --- p.53 / Chapter 3.2.1 --- Results and Discussion --- p.53 / Chapter 3.2.2 --- Mechanistic Studies --- p.61 / Chapter 3.3 --- CHA of Aldehydes by Rh(ttp)+X- --- p.65 / Chapter 3.4 --- Summary --- p.67 / Conclusion --- p.68 / Experimental --- p.69 / Reference --- p.93 / Appendix I Crystal Data and Processing Parameters --- p.99 / List of Spectra --- p.141 / Spectra --- p.143

Base-promoted CHA of unstrained alkanes with 5,10,15,20-tetratolylporphyrinatorhodium complexes, Rh(ttp)X (X = Cl, H, Rh(ttp)), has been achieved. Rh(ttp)Cl, reacted with n-pentane, n-hexane, n-heptane, c-pentane and c-hexane in the presence of potassium carbonate at 120 °C in 6 to 24 h to give rhodium porphyrin alkyls, Rh(ttp)R, in 29--76% yields. Mechanistic investigations suggested that Rh 2(ttp)2 and Rh(ttp)H are key intermediates for the parallel CHA step. The roles of base are (i) to facilitate the formation of Rh(ttp)Y (Y- = OH-, KCO3 -), (ii) to enhance the CHA rate with alkane and generate Rh(ttp)H by a Rh(ttp)Y species which is more reactive than Rh(ttp)Cl, and (iii) to provide a parallel CHA pathway by Rh2(ttp)2. / c-Octane reacted with Rh(ttp)Cl at 120 °C in 7.5 h in the presence of K2CO3 to yield Rh(ttp)( n-octyl) and Rh(ttp)H in 33% and 58% yields, respectively. Mechanistic investigations indicate that the CCA product is generated from the Rh II(ttp)-catalyzed 1,2-addition of c-octane with Rh(ttp)H. Reaction of c-octane and Rh(ttp)H/Rh2(ttp) 2 (10:1) selectively yielded Rh(ttp)(n-octyl) in 73% at 120 °C in 15 h. The catalyst RhII(ttp) radical cleaves the C-C bond of c-octane to form to a Rh(ttp)-alkyl radical, which then abstracts a hydrogen atom from Rh(ttp)H to generate the Rh(ttp)( n-octyl), and subsequently leading to regeneration of the Rh II(ttp) radical. (Abstract shortened by UMI.) / K2CO3-promoted CHA of the ring-strained cycloheptane with Rh(ttp)Cl at 120 °C in 6 h gave the CHA product Rh(ttp)( c-heptyl) and together with, unexpectedly, the CCA product Rh(ttp)Bn, in 30% and 24% yields, respectively. Mechanistic studies revealed that Rh(ttp)( c-heptyl) undergoes beta-hydride elimination in neutral condition or beta-proton elimination in basic condition followed by reprotonation to give rhodium(III) porphyrin hydride, Rh(ttp)H, and c-heptene. Successive base-promoted CHA of c-heptene with Rh(ttp)H, followed by beta-proton elimination, generates cycloheptatriene. The CHA of cycloheptatriene with Rh(ttp)H formed Rh(ttp)(c-heptatrienyl), which underwent rearrangement with carbon-carbon cleavage at 120 °C in 16 d to yield Rh(ttp)Bn in 96% yield. / The objectives of this research focus on the investigation of carbon-hydrogen bond activation (CHA) and carbon-carbon bond activation (CCA) of alkanes by rhodium porphyrin complexes as well as the mechanistic understanding. / Chan, Yun Wai. / Adviser: Kin Shing Chan. / Source: Dissertation Abstracts International, Volume: 73-02, Section: B, page: . / Thesis (Ph.D.)--Chinese University of Hong Kong, 2010. / Includes bibliographical references. / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Electronic reproduction. [Ann Arbor, MI] : ProQuest Information and Learning, [201-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstract also in Chinese.

This thesis studies the yield differential between green bonds and conventional bonds, the so called green premium or "greenium". By deriving a theoretical model that includes investors' preferences for green assets, two hypothesis are formulated: There exists a negative green bond premium and The negative premium is larger in absolute terms in countries with high environmental performance. In order to estimate the premium, synthetic conventional bonds are constructed having the same characteristics as the green bonds. Two different matching methods are used to construct the synthetic bonds, one based on maturity and one based on correlation. The findings of this study suggest a significant negative green premium between -0.29 and -0.78 basis points. Also, the green premium is more than twice as large, in terms of absolute value, if the issuer is based in a country which has a high environmental performance.

Lo, Kwok Cheung. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2009. / Includes bibliographical references (leaves 114-118). / Abstracts in English and Chinese. / Thesis / Assessment Committee --- p.ii / ABSTRACT --- p.iii / ACKNOWLEDGEMENTS --- p.v / TABLE OF CONTENT --- p.vi / Chapter Chapter 1 --- Introduction --- p.1 / Chapter Chapter 2 --- Theoretical Background --- p.5 / Chapter Chapter 3 --- Results --- p.38 / Chapter Chapter 4 --- Discussion and Concluding Remarks --- p.85 / LIST OF TABLES / Table / Table la Electronic energies and geometrical parameters of scandium dicarbide by B3LYP/LANL2DZ and B3LYP/LANL2DZ-d --- p.41 / Table lb Comparison of literature results with current computational results of cyclic scandium dicarbide at equilibrium state by B3LYP/LANL2DZ and B3LYP/LANL2DZ-d --- p.42 / Table lc Comparison of literature results with current computational results of linear scandium dicarbide at equilibrium state by B3LYP/LANL2DZ and B3LYP/LANL2DZ-d --- p.43 / Table 2a Electronic energies and geometrical parameters of titanium --- p.46

yes / Professionals working with patients at end of life need to feel comfortable and confident discussing death, dying and bereavement (DDB), however this is not always the case.1 2 The Continuing Bonds Project sought to explore the impact of archaeology on the confidence and comfort for health and social care professionals and students in talking about DDB.

The syntheses of a new class of polycyclic TriAmino DiCarbenes (TADCs), based on 3,9-diazajulolidine, and their precursors and adducts are described. Starting with 2,6-dimethyl-nitrobenzene, 2,6-bis ((alkylamino)methyl)anilines (alkyl = isopropyl, mesityl, and tert-butyl) were synthesized in 40% yield over five steps. These triamines were then di-cyclized stepwise to diformamidinium dications or formamidinium/2-methoxyformaminals using oxonium salts and trialkyl orthoformates. A diformamidinium dication was characterized by single-crystal X-ray diffractometry. Treatment with various bases, particularly lithium hexamethyldisilylazide, led to the novel TADCs and monocarbenes, two of which were isolated and characterized by 1H and 13C NMR spectroscopies. In both cases, treatment with elemental sulfur trapped the TADCs as dithiobiurets. No TADC-transition metal complexes were successfully isolated from reactions of the diformamidinium dications or LiHMDS TADC complex with a number of transition metal complexes. With the exception of these two cases, all other TADCs were not isolated because they rapidly reacted to form dimers, trimers, and tetramers. One of these dimers was isolated and its structure determined using 1D and 2D NMR spectroscopies, along with high-resolution electrospray ionization mass spectrometry. This revealed that the TADC had dimerized to form an ene-triamine, likely via 1,3-shift of a benzylic proton. Novel N-heterocyclic Carbene (NHC) complexes of molybdenum were also synthesized and characterized. Reaction of Cp2Mo2(CO)4 (Cp = C5H5) with dimesityl-imidazol-2-ylidenes (IMes) or dimesityl-imidazolidin-2-ylidenes (SIMes) yielded the molybdoradicals CpMo(CO)2(NHC) (NHC = IMes or SIMes). The carbonyl infrared stretching frequencies and the relative metal-to-NHC π-backbonding for IMes and SIMes complexes are compared. Reaction of the less bulky dimethyl-imidazol-2-ylidene (IMe) with Cp2Mo2(CO)4 yielded the Mo-Mo triple bond complex Cp2Mo2(CO)3(IMe) by CO substitution. This is the first example of an NHC-ligated metal-metal multiply bonded complex. Single crystal X-ray diffractometry of these new organomolybdenum and organodimolybdenum complexes is discussed.

I examined male endocrinology and social bonds in relation to dominance status in four groups of wild white-faced capuchin monkeys, Cebus capucinus, in the Santa Rosa Sector of the Área de Conservación Guanacaste, Costa Rica. I used noninvasive monitoring of male fecal androgen and glucocorticoid levels to examine the hormonal correlates of dominance and rank acquisition. In spite of low rates of aggression among coresident males, alpha males had higher androgen (testosterone and dihydrotestosterone) levels than subordinate males. Among subordinates, adult males had higher androgen levels than subadult males. During a non-aggressive rank increase, the new alpha male’s androgen levels increased immediately after attainment of the alpha position, and continued to increase for several months thereafter, while glucocorticoid increases lagged behind. In contrast, a subordinate adult male in the group had no change in androgen or glucocorticoid levels. Female white-faced capuchins do not display behavioral estrus, and ovulation is not associated with any changes detectable to the human observer. Therefore, I inferred female reproductive status by analyzing fecal progesterone and estradiol. Alpha and subordinate males experienced androgen and glucocorticoid increases in the presence of fertile females, a period likely associated with increased sexual activity and competition among coresident males. Androgens and glucocorticoids were also higher in the dry season, when intergroup encounters were more frequent. High competition between groups may facilitate low rates of intragroup aggression and the formation of social bonds within groups. I found that coresident males formed differentiated social bonds, and formed stronger social bonds when they had fewer coresident males and when group sex ratio was male-biased. Alpha males had the weakest and least equitable bonds, while relationships among subordinate males were characterized by relatively strong and somewhat reciprocal grooming. The importance of male bonds, particularly among subadult males, may reflect the importance of coalitions of immigrant males in the ability to takeover social groups and increase dominance status. A meta-analysis of parallel dispersal – when conspecifics emigrate together or immigrate into groups containing familiar individuals - indicates that in male primates, this behavior may be linked with the propensity of males to form coalitions and the need to retain coalition partners. / acase@tulane.edu

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