He Left the Same as He Entered

In lieu of an abstract, below is the essay\u27s first paragraph. Greg walked into the office as he did everyday, setting his lunch down on the shiny metal table that sat adjacent to the door. Calling this place an office was an obvious stretch, but it was better than referring to it as the Dead Drop-off, as the other coroner Bruce always refers to it. Every time the cops stopped by, they would remark about how absurd it was to call it the Coroner\u27s office. They always mused at Bruce\u27s not-so-subtle nickname

All In A Day\u27s Walk

In lieu of an abstract, below is the essay\u27s first paragraph. There was a man who used to walk down the street everyday in the city. He always minded his own business, never saying a word to anyone. He would leave his apartment at 4:00 pm., and walk for exactly half an hour, returning home at 4:30 pm. The neighbor hood kids would make fun of him, but he never replied, and they would leave him alone after a couple of minutes

Syntheses, molecular structures, and fiber-optic infrared spectroelectrochemistry of nitrosyl metalloporphyrins containing axially bound alkoxide, thiolate, imidazole, and imidazolate ligands.

This dissertation describes the syntheses, molecular structures, and infrared spectroelectrochemistry of nitrosyl ruthenium and osmium porphyrins containing axially bound alkoxide, thiolate, imidazole, and imidazolate ligands.Chapter 3 describes the syntheses of the neutral and cationic (por)Ru(NO)(RIm) (por = TPP, TTP, T(p-OMe)PP), OEP; RIm = imidazolate (Im), imidazole (HIm), 1-methylimidazole (1-MeIm), 4-methylimidazole (4-MeHIm), 5-methylimidazolate (5-MeIm), and 5-methylimidazole (5-MeHIm)) compounds. The neutral imidazolate (por)Ru(NO)(RIm) (R = nothing, 4-Me) complexes were prepared from the addition of the corresponding RHIm to (por)Ru(NO)(O- i-C5H11). The cationic imidazole [(por)Ru(NO)(RIm)] + complexes were prepared from the solvent-free addition of RHIm (R = nothing, 1-Me, 4-Me) to the precursor [(por)Ru(NO)]+ complex. Both the neutral imidazolate and cationic imidazole complexes were characterized by IR and 1H NMR spectroscopy, and by FAB or ESI mass spectrometry. The IR spectra (in CH2Cl2) of the neutral imidazolate complexes displayed nuNO bands in the 1845--1855 cm-1 range, while the cationic imidazole complexes displayed similar bands in the 1854--1877 cm-1 range. Bands in these ranges are suggestive of linear NO ligands in these types of complexes. The 1H NMR spectra of the product that resulted from addition of 4-methylimidazole to [(OEP)Ru(NO)]+ resulted in two sets of peaks that were assigned to the structurally isomeric [(OEP)Ru(NO)(4-MeHIm)]+ and [(OEP)Ru(NO)(5-MeHIm)] + complexes. Further, we were able to determine that the less sterically stable 4-MeHIm containing isomer undergoes a first order dissociation of the 4-MeHIm ligand from the Ru center with the rate constant (k) of 1.44 x 10-5 s-1 with a half-life (t1/2) of 4.81 x 104 s. This was followed by the rebinding of the ligand to the metal center to form the [(OEP)Ru(NO)(5-MeHIm)]+ isomer. The solid-state crystal structures of the imidazolate and imidazole adducts of the (OEP)Ru(NO) complexes were determined by single-crystal X-ray crystallography.Chapter 2 describes the syntheses of (OEP)Ru(NO)(XR) (XR = OEt, SEt, S-i-C5H11, SPh) complexes and the redox behavior of the osmium and ruthenium compounds (OEP)M(NO)(OEt) and (OEP)M(NO)(SEt) (M = Os, Ru), as determined by cyclic voltammetry and infrared spectroelectrochemistry. The (OEP)Ru(NO)(XR) complexes were prepared in 61--85% yields through the formal trans addition of RSNO to (OEP)Ru(CO) with loss of CO. These nitrosyl alkoxide and thiolate complexes were characterized by IR and 1H NMR spectroscopy, and by ESI mass spectrometry. Infrared spectroelectrochemical studies revealed that the (OEP)Os(NO)(OEt) compound undergoes a single reversible oxidation process in dichloromethane. In contrast, the thiolate compound (OEP)Os(NO)(SEt) undergoes a net irreversible oxidation resulting in formal loss of the SEt ligand. Extended Huckel calculations on crystal structures of these two compounds provide insight into the nature of their HOMOs. In the case of the alkoxide compound, the HOMO is largely metalloporphyrin centered. However, the HOMO of the thiolate compound consists of a pi bonding interaction between the metal dxz orbital and the px orbital on the sulfur, and a pi antibonding interaction between the metal d orbital and a pi* orbital on NO. The redox behavior of the Ru analogues have been determined, and are compared with those of the Os compounds.Chapter 4 describes the electrochemistry and infrared spectroelectrochemistry of (OEP)Ru(NO)(Im) and [(OEP)Ru(NO)(RIm)]+ (R = H, 1-Me). Electrochemical oxidation of the (OEP)Ru(NO)(Im) complex in CH2Cl2 displayed a partially reversible single electron transfer centered on the porphyrin followed by an apparent radical hydrogen extraction from the solvent by the nitrogen atom of the imidazolate ring to form the cationic [(OEP)Ru(NO)(HIm)] + derivative. The [(OEP)Ru(NO)(HIm)]+ and [(OEP)Ru(NO)(1-MeIm)] + complexes, on the other-hand, exhibit porphyrin based reversible single electron transfers upon oxidation. However, the reduction of the [(OEP)Ru(NO)(HIm)] + complex proceeds through a partially reversible single electron transfer followed by an apparent H· extraction from the nitrogen atom of the imidazole by the solvent system to form the neutral (OEP)Ru(NO)(Im) derivative. The reduction of the 1-MeIm complexes proceeds through a partially reversible single electron transfer that was followed by the loss of the bond between 1-MeIm ligand the ruthenium center of the porphyrin. Extended Huckel calculations on crystal structures of the (OEP)Ru(NO)(Im) and [(OEP)Ru(NO)(HIm)]+ complexes provides insight on their redox properties. The calculated HOMOs for the isoelectronic structures show charge centered on the porphyrin, providing supporting evidence for the generation of porphyrin-centered pi-radical cations upon oxidation. The calculated LUMO of the cationic complex, however, suggests that the reduction first occurs on the metal-nitrosyl fragment of the [(OEP)Ru(NO)(HIm)] + complex, increasing the antibonding interaction between the metal dxz and pi*. orbital on NO. Presumably, the resulting unfavorable bent Ru-NO- like geometry is relieved by an electronic rearrangement that leads to the extraction of H· from the nitrogen of the imidazole by the solvent system.Chapter 1 introduces the fundamental issues involved in the chemistry of Group 8 Fe, Ru, and Os nitrosyl porphyrin complexes with trans and O- and S-bound ligands, imidazole, and pyridine and their derivatives. Additionally, this chapter introduces important aspects of the biochemistry of the relevant nitrosyl adducts of heme proteins

The Role of Language Interpretation in Providing a Quality Mediation Process

This paper focuses on the role of language in mediation and the challenges multiple language fluencies bring to the practice. Beginning with a discussion of the process and ethics of mediation as a form of alternative dispute resolution, as distinct from other forms of dispute resolution including arbitration, the paper shifts to consider the importance of language. Language, and more specifically interpretation, plays a central role in the integrity of the mediation process and the quality of its outcomes. Each stage of mediation requires the participants and the mediator understand one another to ensure effective communication and a quality process. The most essential principles of mediation: self-determination, impartiality, and confidentiality, cannot be upheld when participants are unable to understand one another. Addressing language interpretation issues in mediation requires ensuring that interpreters with proper training and expertise are hired to assist in mediations. The interpreter should be a neutral and impartial third party. The mediator should be allotted additional time in a session for thorough and accurate language interpretation to ensure satisfying and sustainable solutions for participants

Choose to Live

In lieu of an abstract, below is the essay\u27s first paragraph. The sky was a dark and gloomy gray; I expected the rain to start falling at any moment. I stared at my father\u27s unmoving body, draped in his best suit. His face bore the same unhappy look that I had always been accustomed to. I had always felt that my father would rather be dead, because he never really seemed to enjoy life