Self-Supported N-Heterocyclic Carbenes and Their Use as Organocatalysts

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Chromatography-Free Esterification Reactions Using a Bifunctional Polymer

A linear polystyrene functionalized with both nucleophilic DMAP groups and sterically hindered tertiary amine groups was synthesized and used homogeneously in a range of esterification reactions between alcohols and various carboxylic acid derivatives. The polymer was highly effective in such reactions where the DMAP groups served as catalytic groups. The ester products of these reactions could be isolated in high purity and yield without the need for chromatographic purification, and the polymer could be recovered and reused numerous times with no apparent decrease in utility.postprin

Behavioral and molecular mechanisms of pheromone transmission in the honey bee (Apis mellifera)

The European honey bee (Apis mellifera) has a sophisticated system of pheromonal signals that mediate a wide range of behaviors important for their fitness, including reproductive dominance, nest defense, and cooperative brood care. In honey bees, there are two distinct pheromones emitted by larvae, brood pheromone and (E)-beta-ocimene. By integrating behavior, chemical ecology, and transcriptomics, this dissertation analyzes several key stages in signal transmission in a systematic effort to understand how these two pheromones affect behavior, and in the process, generates a synthetic understanding of a highly complex system of communication. Previous studies have explored behavioral and gene expression patterns related to honey bee pheromones; however, none have compared the roles that two divergent pheromones from a common source play in rapid regulation of foraging behavior. Furthermore, while previous studies have investigated the mechanisms of pheromone detection and the factors involved in regulation of foraging behavior, it remains unclear how individual responses to pheromone exposure scales to colony-level changes in behavior. By investigating the behavioral, physiological, and genomic influences of honey bee chemical communication, this dissertation links phenotypic plasticity in behavior to gene expression profiles in the brain and provides insights into the evolution of a sophisticated chemical language.Ecology, Evolution and Behavio

Development of Absorption and Fluorescence Probes Based on Mouse Model for Molecular Optical Imaging [abstract]

Comparative Medicine - OneHealth and Comparative Medicine Poster SessionIn this work we summarize our collaborative research on a project to develop absorption and fluorescence targeting probes. Several groups from University of Missouri and Harry S. Truman Memorial Veteran's Hospital including Dr. Ma's group, Dr. Yu's group, Dr. Smith's group, Dr. Hoffman's group, and Professor Wynn Volkert have been involved in the project. Our goal is to develop probes based on mouse model for molecular optical imaging. In vivo imaging of targeted fluorescence molecular probes, or molecular imaging, is an emerging field in biomedical imaging. During the past forty years, three dimensional biomedical imaging technologies such as CT and MRI have been extensively used in human health and diseases. However, the human body is a complex and interactive biological system. A fundamental scientific barrier in previous biomedical imaging technologies is their limited ability to study physiological processes in vivo at the cellular and molecular levels. Molecular imaging technologies can overcome this barrier. Optical imaging modalities have the highest sensitivity compared to other imaging techniques. So they are good candidates for molecular imaging. We develop probes for two biomedical optical imaging techniques. The first technique is coherence domain imaging. This technique can be used to monitor interactions between targeted peptide conjugates and cancer cells at a tissue level. It requires absorption properties of the probe for effective molecular imaging. The second technique is fluorescence mediated tomographic imaging using an image-intensified CCD camera. This technique uses fluorescence of the probe for molecular imaging. Dye bombesin conjugates are synthesized for site-specific absorption and fluorescence imaging in human prostate and breast cancer cells. Bombesin (BBN), an amphibian analog to the endogenous ligand, binds to the gastrin releasing peptide receptors (GRPr) with high specificity and affinity. BBN conjugates have a specific significance in cancer detection and therapy due to high over-expression levels of GRPrs in human cancer cells. Previously, we have developed an Alexa Fluor 680 BBN peptide conjugate. This probe can not be used as an absorption probe in near-infrared imaging since its absorption peak is in the visible wavelength range. In addition, long wavelength fluorescence is desired because long wavelength photons can penetrate deeper into tissue when using the conjugates as a fluorescent probe. The new absorption and fluorescent probe we developed is based on the last eight-residues of BBN and labeled with Alexa Fluor 750 through an effective linker. The developed probe, AF750-BetaAla-BBN[7-14]NH2, exhibits optimal pharmacokinetic properties for targeting GRPr over-expressing cancer cells in mice. Absorption spectra have been measured and showed absorption peaks at 690nm, 720nm and 735nm. Fluorescent band is located at 755nm. Fluorescent microscopic imaging of the conjugates in human PC-3 prostate cancer and T-47D breast cancer cells indicated specific uptake and internalization in vitro. In vivo optical and MR imaging was performed in SCID mice bearing human breast and prostate xenografts. In vitro and in vivo studies have demonstrated the effectiveness of the fluorescent probe Alexa Fluor 750-BetaAla-BBN[7-14]NH2 to specifically target GRPr overexpressed cancer tissues

Rasta Resin-TBD-Catalyzed γ-Selective Morita–Baylis–Hillman Reactions of α,γ-Disubstituted Allenones

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Heterotopic heart transplantation in the rat receiving FK-506 alone or with cyclosporine.

In rats, FK significantly prolonged heterotopic heart graft survival over a wide dose range when given for 2 weeks starting on the day of the operation. Brief courses of FK for one to four days preoperatively, and especially beginning four days postoperatively, allowed long subsequent survival of heart grafts in otherwise untreated recipients. The seeming acceptance of the grafts with postoperative FK treatment was largely but not exclusively donor specific when tested eight days after the last FK dose by second grafts from the same donor v third-party donor grafts. FK in minimally therapeutic doses was synergistic with suboptimal doses of CyA

Hypothalamic actions of neuromedin U.

The central nervous system and gut peptide neuromedin U (NMU) inhibits feeding after intracerebroventricular injection. This study explored the hypothalamic actions of NMU on feeding and the hypothalamo-pituitary-adrenal axis. Intraparaventricular nucleus (intra-PVN) NMU dose-dependently inhibited food intake, with a minimum effective dose of 0.1 nmol and a robust effect at 0.3 nmol. Feeding inhibition was mapped by NMU injection into eight hypothalamic areas. NMU (0.3 nmol) inhibited food intake in the PVN (0-1 h, 59 ± 6.9% of the control value; P < 0.001) and arcuate nucleus (0-1 h, 76 ± 10.4% of the control value; P < 0.05). Intra-PVN NMU markedly increased grooming and locomotor behavior and dose-dependently increased plasma ACTH (0.3 nmol NMU, 24.8 ± 1.9 pg/ml; saline, 11.4 ± 1.0; P < 0.001) and corticosterone (0.3 nmol NMU, 275.4 ± 40.5 ng/ml; saline, 129.4 ± 25.0; P < 0.01). Using hypothalamic explants in vitro, NMU stimulated CRH (100 nM NMU, 5.9 ± 0.95 pmol/explant; basal, 3.8 ± 0.39; P < 0.01) and arginine vasopressin release (100 nM NMU, 124.5 ± 21.8 fmol/explant; basal, 74.5 ± 7.6; P < 0.01). Leptin stimulated NMU release (141.9 ± 20.4 fmol/explant; basal, 92.9 ± 9.4; P < 0.01). Thus, we describe a novel role for NMU in the PVN to stimulate the hypothalamo-pituitary-adrenal axis and locomotor and grooming behavior and to inhibit feeding