Medicine and Health Sciences Commons^™

Phosphate Esters, Thiophosphate Esters And Metal Thiophosphates As Lubricant Additives, David W. Johnson, John E. Hils

Chemistry Faculty Publications

Phosphate esters, thiophosphate esters and metal thiophosphates have been used as lubricant additives for over 50 years. While their use has been extensive, a detailed knowledge of how they work has been a much more recent development. In this paper, the use of phosphate esters and thiophosphate esters as anti-wear or extreme pressure additives is reviewed with an emphasis on their mechanism of action. The review includes the use of alkyl phosphates, triaryl phosphates and metal containing thiophosphate esters. The mechanisms of these materials interacting with a range of iron and steel based bearing material are examined.

Recruitment Of Tlr Adapter Trif To Tlr4 Signaling Complex Is Mediated By The Second Helical Region Of Trif Tir Domain, Wenji Piao, Lisa W. Ru, Kurt H. Piepenbrink, Eric J. Sundberg, Stefanie N. Vogel, Vladimir Y. Toshchakov

Food for Health: Publications

Toll/IL-1R resistance (TIR) domain–containing adapter-inducing IFN-β (TRIF) is a Toll-like receptor (TLR) adapter that mediates MyD88-independent induction of type I interferons through activation of IFN regulatory factor 3 and NFκB. We have examined peptides derived from the TRIF TIR domain for ability to inhibit TLR4. In addition to a previously identified BB loop peptide (TF4), a peptide derived from putative helix B of TRIF TIR (TF5) strongly inhibits LPS-induced cytokine and MAPK activation in wild-type cells. TF5 failed to inhibit LPS-induced cytokine and kinase activation in TRIF-deficient immortalized bone-marrow–derived macrophage, but was fully inhibitory in MyD88 knockout cells. TF5 does …

Structure, Theoretical Studies And Coupling Reactions Of Some New Cyclic Boronic Esters, Andrew Kuttler, Sravanthi Durganala, Albert Fratini, Alexander Morgan, Vladimir Benin

Chemistry Faculty Publications

The present report describes the X-ray structural and theoretical studies of some new pinacolboronate esters, and it also outlines the use of the target structures in Suzuki coupling reactions to produce new aromatic or heteroaromatic esters and amides. X-ray structural analysis of the studied compounds revealed that the pinacolborane ring's position with respect to the benzene ring varies, depending on the particular environment. An ortho-positioned carboxylic ester (methyl ester) causes a nearly perpendicular orientation of the pinacolborane unit with respect to the benzene ring, whereas an ortho-positioned amide (N,N-dimethylamide) causes the pinacolborane unit to orient itself nearly coplanar. A plausible …

Effects Of Prior Acute Exercise On Circulating Cytokine Concentration Responses To A High-Fat Meal, Josef Brandauer, Rian Q. Landers-Ramos, Nathan T. Jenkins, Espen E. Spangenburg, James M. Hagberg, Steven J. Prior

Health Sciences Faculty Publications

High-fat meal consumption alters the circulating cytokine profile and contributes to cardiometabolic diseases. A prior bout of exercise can ameliorate the triglyceride response to a high-fat meal, but the interactive effects of exercise and high-fat meals on cytokines that mediate cardiometabolic risk are not fully understood. We investigated the effects of prior exercise on the responses of circulating tumor necrosis factor-a (TNF-a), interleukin-6 (IL-6), IL-8, leptin, retinol-binding protein 4 (RBP4), vascular endothelial growth factor (VEGF), basic fibroblast growth factor (bFGF), placental growth factor (PlGF), and soluble fms-like tyrosine kinase-1 (sFlt-1) to a high-fat meal. Ten healthy men were studied before …

Characterization By Nmr Of Reactants And Products Of Hydrofluoroether Isomers, Cf3(Cf2)3och3 And (Cf3)2c(F)Cf2och3, Reacting With Isopropyl Alcohol, Howard Knachel, Vladimir Benin, William E. Moddeman, Janine C. Birkbeck, Thomas A. Kestner, Tayna L. Young

Chemistry Faculty Publications

The 3M Company product Novec™ 71IPA DL, a mixture of methoxyperfluorobutane, methoxyperfluoroisobutane and 4.5 wt.% isopropyl alcohol, has been found to be very stable at ambient temperature, producing fluoride at the rate of ~1 ppm/year. Our earlier kinetic and theoretical studies have identified the reaction mechanism. This paper identifies the ¹H and ¹⁹F NMR chemical shifts, multiplicities, and coupling constants of reactants and the major products that result from aging the mixture in sealed Pyrex NMR tubes for periods up to 1.8 years at temperatures from 26 °C to 102 °C. Chemical shifts and coupling constants of fluorine …

Human Milk Cortisol Is Associated With Infant Temperament, Katherine R. Grey, Elyssia Poggi Davis, Curt A. Sandman, Laura M. Glynn

Psychology Faculty Articles and Research

The implications of the biologically active elements in milk for the mammalian infant are largely unknown. Animal models demonstrate that transmission of glucocorticoids through milk influences behavior and modifies brain development in offspring. The aim of this study was to determine the relation between human milk cortisol levels and temperament of the breastfed infant. Fifty-two mother and infant pairs participated when the infants were three-months old. Milk cortisol levels were assessed and each mother completed the Infant Behavior Questionnaire (IBQ), a widely used parent-report measure of infant temperament. Analyses revealed a positive association between milk cortisol and the negative affectivity …

Methods For Quantifying T Cell Receptor Binding Affinities And Thermodynamics, Kurt H. Piepenbrink, Brian E. Gloor, Kathryn M. Armstrong, Brian M. Baker

Food for Health: Publications

αβ T cell receptors (TCRs) recognize peptide antigens bound and presented by class I or class II major histocompatibility complex (MHC) proteins. Recognition of a peptide/MHC complex is required for initiation and propagation of a cellular immune response, as well as the development and maintenance of the T cell repertoire. Here we discuss methods to quantify the affinities and thermodynamics of interactions between soluble ectodomains of TCRs and their peptide/MHC ligands, focusing on titration calorimetry, surface plasmon resonance, and fluorescence anisotropy. As TCRs typically bind ligand with weak-to-moderate affinities, we focus the discussion on means to enhance the accuracy and …

Investigating Obesity Risk-Reduction Behaviours And Psychosocial Factors In Chinese Americans, Yeon Bai, Doreen Liou, Kathleen D. Bauer

Department of Nutrition and Food Studies Scholarship and Creative Works

AIM: The purpose of this research was to examine the attitudes, beliefs, and behaviors related to obesity risk reduction in Chinese Americans.

METHODS: A questionnaire was administered to a convenience sample of 300 US-born and foreign-born Chinese Americans residing in the New York metropolitan area, ranging from 18 to 40 years of age. Obesity risk reduction behaviors and psychosocial variables derived from the Theory of Planned Behaviour and Health Belief Model were measured. Acculturation was assessed using a modified Suinn-Lew Asian Self-Identity Acculturation Scale. Frequency distributions were delineated and stepwise regression analyses were analyzed for different acculturation groups.

RESULTS: 65% …

Cinacalcet As Adjunctive Therapy For Hereditary 1,25-Dihydroxyvitamin D-Resistant Rickets., Tarak Srivastava, Uri S. Alon

Manuscripts, Articles, Book Chapters and Other Papers

Secondary hyperparathyroidism from inadequate calcium absorption in the gut, is the underlying pathophysiology for rachitic changes in hereditary vitamin D-resistant rickets (HVDRR). We describe a novel use of Cinacalcet to treat a child with HVDRR in whom conventional modes of therapy had to be discontinued. Cinacalcet therapy with high-dose oral calcium effectively normalized the metabolic abnormalities and bone condition. The relative ease of administration of the calcimimetic as a once- or twice-daily oral preparation, compared with traditional intravenous calcium administration, should encourage its move to the frontline of treatment of the disorder.

Interaction Between Lubricants Containing Phosphate Ester Additives And Stainless Steels, David W. Johnson, Matthew Bachus, John E. Hils

Chemistry Faculty Publications

One way to improve fuel efficiency in today’s jet aircraft engines is to create an environment for higher operating temperatures and speeds. New and improved lubricants and bearing materials must be developed to remain stable in these elevated operating temperatures. Three lubricants, with varying amounts of tricresyl phosphate added as an anti-wear/extreme pressure additive were tested on two different stainless steels at varying temperatures ranging from 300 °C to 350 °C in vacuum. Significant decomposition of the lubricant base-stocks and the phosphate ester additive did occur in most of the trials resulting in the formation of carboxylic acids and phenols. …

Holobiont Nutrition: Considering The Role Of The Gastrointestinal Microbiota In The Health Benefits Of Whole Grains, Jens Walter, Ines Martinez, Devin J. Rose

Food for Health: Publications

Intake of whole grains and other food products high in dietary fiber have long been linked to the prevention of chronic diseases associated with inflammation. A contribution of the gastrointestinal microbiota to these effects has been suggested, but little is known on how whole grains interact with gut bacteria. We have recently published the first human trial that made use of next-generation sequencing to determine the effect of whole grains (whole grain barley, brown rice or a mixture of the two) on fecal microbiota structure and tested for associations between the gut microbiota and blood markers of inflammation, glucose and …

Fiber-Free White Flour With Fructose Offers A Better Model Of Metabolic Syndrome, Faridah Amin, Anwar Hassan Gilani

Department of Biological & Biomedical Sciences

BACKGROUND: The metabolic syndrome (MS) is a combination of metabolic abnormalities that lead to an increased risk of cardiovascular diseases. Due to its rising incidence and demanding life-long use of multiple drugs, there is a growing interest in testing and developing new allopathic, complementary and alternative therapies for controlling or curing disorders of MS. The discovery of new therapeutic modalities requires animal models of disease and currently available models have limitations. Developing an appropriate animal model for MS to achieve various therapeutic targets remains a challenge and this study aims to develop a rat model which closely depicts MS in …

The Healthy Incentive For Pre-Schools (Hip) Project: The Development, Validation, Evaluation And Implementation Of An Healthy Incentive Scheme In The Irish Full Day Care Pre-School Setting., Charlotte Johnston Molloy

Doctoral

While many children are now cared for outside the home, inadequate nutrition and physical activity practices in pre-schools have been reported. This study aimed to develop a validated nutrition and health related evaluation tool and an education information resource for pre-schools, and determine whether their use can promote improved food service and nutrition and physical activity practices in this setting. Following a pilot phase undertaken in Co. Wicklow (n 12), pre-schools providing a full day care service in the Midland Area of Ireland were invited to participate in the study (n, 100). Direct observation was used to collect data (food …

Control Of Candida Albicans Metabolism And Biofilm Formation By Pseudomonas Aeruginosa Phenazines, Diana K. Morales, Nora Grahl, Chinweike Okegbe, Lars E. P. Dietrich, Nicholas J. Jacobs, Deborah A. Hogan

Dartmouth Scholarship

Candidaalbicanshasdevelopmentalprogramsthatgoverntransitionsbetweenyeastandfilamentousmorphologies and between unattached and biofilm lifestyles. Here, we report that filamentation, intercellular adherence, and biofilm develop- ment were inhibited during interactions between Candida albicans and Pseudomonas aeruginosa through the action of P. aeruginosa-produced phenazines. While phenazines are toxic to C. albicans at millimolar concentrations, we found that lower concentrations of any of three different phenazines (pyocyanin, phenazine methosulfate, and phenazine-1-carboxylate) allowed growth but affected the development of C. albicans wrinkled colony biofilms and inhibited the fungal yeast-to-filament transition. Phenazines impaired C. albicans growth on nonfermentable carbon sources and led to increased production of fer- mentation products (ethanol, glycerol, and …

Preparation Of Phosphonoterephthalic Acids Via Palladium-Catalyzed Coupling Of Aromatic Iodoesters, Nathaniel Ivan, Vladimir Benin, Alexander Morgan

Chemistry Faculty Publications

The current article reports in detail the preparation of two phosphonoterephthalic acids: 2-phosphonoterephthalic acid (1) and 2,5-diphosphonoterephthalic acid (2). Efficient, scalable syntheses have been developed for both compounds based on Pd-catalyzed coupling reactions of iodinated terephthalate esters. Phosphonoterephthalic acids are potentially useful as flame-retardant additives or as monomers for the construction of acid-pendant polymer chains.

Reaction Between Polyol-Esters And Phosphate Esters In The Presence Of Metal Carbides, David W. Johnson, Carolyn Iacullo, John E. Hils

Chemistry Faculty Publications

The reaction of metal carbides with polyol esters found in aerospace lubricants and phosphate esters commonly used as additives was investigated. Carbides were of particular interest since modern materials under consideration at high temperature bearings have surfaces that are primarily metal carbides. Vanadium and chromium carbide were found to react with the ester and phosphate ester by a transesterification reaction, producing an alkyl phosphate which is less stable than the aromatic phosphate esters. In the process, the metal carbide is converted to the metal phosphate and metal polyphosphate, evidenced by the infrared and Raman spectra of the solid residue and …

Development And Validation Of A Predictive Model Of Acute Glucose Response To Exercise In Individuals With Type 2 Diabetes, Bryan S. Gibson, Sheri R. Colberg, Paul Poirier, Denise Maria Martins Vancea, Jason Jones, Robin Marcus

Human Movement Sciences & Special Education Faculty Publications

Background: Our purpose was to develop and test a predictive model of the acute glucose response to exercise in individuals with type 2 diabetes.

Design and methods: Data from three previous exercise studies (56 subjects, 488 exercise sessions) were combined and used as a development dataset. A mixed-effects Least Absolute Shrinkage Selection Operator (LASSO) was used to select predictors among 12 potential predictors. Tests of the relative importance of each predictor were conducted using the Lindemann Merenda and Gold (LMG) algorithm. Model structure was tested using likelihood ratio tests. Model accuracy in the development dataset was assessed by leave-one-out cross-validation. …