Twenty untrained men (18-25 y) were assigned to consume either a milk supplement (MILK) or a carbohydrate-electrolyte supplement (CHO) immediately following each resistance workout during a 10 wk resistance training program. Subjects trained 3 d/wk beginning with an intensity of 55% 1-RM and progressing to 97% 1-RM by wk 10. Muscle strength (1-RM), body composition (DEXA) and resting, fasted serum concentrations of total and free testosterone and IGF-1 were measured pre- and post-training. CHO tended to reduce, while MILK increased body weight (P = 0.10). All subjects significantly reduced percent body fat (1.1%) and significantly increased lean body mass (1.21 kg) as a result of the resistance training with no significant differences between treatments. However, MILK tended to increase lean body mass (P = 0.1) more than CHO (1.6 and 0.8 kg, respectively). About 39% of lean mass gain for all subjects was in the leg region, while the arms accounted for about 28% of lean gain. Resistance training also caused a similar significant 44% increase in muscle strength for the seven exercises combined for both groups. Resting total and free testosterone concentrations significantly decreased from baseline values in both groups of subjects (16.7% and 11%, respectively), while resting insulin concentrations significantly increased in all subjects (P<0.01). There were no significant changes in resting, fasted IGF-1 concentrations. In summary, dietary supplementation with a MILK or CHO beverage immediately following resistance exercise resulted in similar changes in muscle strength and hormone concentrations following a 10 wk periodized resistance training program. MILK tended to increase body weight and lean body mass more so than CHO. / Master of Science

This study examined the effects of carbohydrate supplementation on resistance exercise performance, cortisol levels, and creatine kinase levels in trained males undergoing energy restriction. Sixteen experimental subjects were randomly assigned to a carbohydrate (C, n=8) or placebo group (P, n=8). The remaining six subjects served as controls (N). Performance tests were done before (Trials 1 and 2) and after (Trial 3) energy restriction. Experimental subjects consumed a low calorie formula diet for three days (18 kcal-1 kg-1 d-1). They had blood drawn before and after T2 and T3. For T3, they consumed either a carbohydrate (1g kg-1) or a placebo beverage 30 minutes before exercise. There was a significant increase in resting cortisol levels following energy restriction. CK levels were significantly elevated after exercise, suggestion muscle damage. Carbohydrate supplementation had no effect on blood glucose, cortisol, creatine kinase, or RPE. The number of repetitions performed during the final set of bench press showed significant interaction between groups and time. P and N increased the number of repetitions performed from T2 to T3 (15.0 + 1.4 to 17.3 + 0.8 for P, 15.0 + 2.7 to 16.7 + 2.3 for N). C decreased the number of repetitions performed 17.6 + 0.7 to 17.3 + 1.0). The number of repetitions performed during the final set of leg extensions showed no interaction between groups and time (p=0.801). This study did not support a benefit of consuming carbohydrate prior to resistance exercise for dieting athletes but illustrates that energy restriction increases a catabolic hormone. / Master of Science

PolySialic acid (polySia) is a linear carbohydrate homopolymer of α- 2,8-linked sialic acids and a posttranslational modification of NCAM (neural cell adhesion molecule), biosynthesized by combined action of two polysialyltransferase enzymes, ST8SiaIV(PST) and ST8SiaII(STX). PolySia alters NCAM-dependent cell adhesion that is crucial for the CNS development. In adulthood, polySia expression is largely absent persisting only in areas of the brain associated with neuronal plasticity. Significantly, a number of malignant tumours re-express polySia and there is considerable evidence that its presence is related to higher malignancy, invasion and metastasis. The hypothesis underpinning this project is that inhibition of polySia biosynthesis will prevent (or reduce) tumour cell migration and invasion, thereby reducing the incidence of metastasis, which will lead to higher patient survival. The work reported in this thesis describes efforts towards the synthesis polysialyltransferase inhibitors that are structural analogues of CMP-Neu5Ac, the natural substrate. Specifically, development of methodology to synthesise building blocks suitable for conjugation as inhibitors is described. Quinic acid-based substrate analogues were explored, with a focus on development of chemistry to achieve substitution of C1-OH. Several protected quinic acid-based compounds were synthesized, and deoxygenation of the C1-OH through the use of a Barton-McCombie reaction was accomplished successfully, allowing an attempt to introduce different aliphatic groups at C1 position using the Mukayiama reaction. Synthesis of a cytidine building block, suitable for conjugation to either quinic acid or sialic acid is also reported. In parallel, studies towards the development of sialoside disulfide analogues are described, with novel conditions identified for their synthesis.

Polyamides are versatile polymers and includes naturally occurring macromolecules such as proteins as well as purely synthetic materials such as Nylon-3 and Nylon-6 polymers. While there are different ways to prepare polyamides, polyamide synthesis using anionic ring opening polymerization of lactams is the most widely used technique, due to the ease in preparation, excellent control in molecular weight and availability of wide variety of monomers. Our group reported the preparation of carbohydrate-based polyamides called poly-amido-saccharides (PASs) using anionic ring opening polymerization of sugar b-lactam monomers. The PASs reported so far includes glucose, galactose, altrose and maltose PASs, and functional PASs with n-octyl, carboxylate and amine functionalities. Sulfated or block poly-amido-saccharides on the other hand are unknown. In this thesis, I describe the synthesis of sulfated and block poly-amidosaccharides as well as evaluation of their biomedical applications. Naturally occurring sulfated polysaccharides play important roles in anticoagulation, lubrication of cartilage, and in developmental processes. New glucose-based non-regioselectively and regioselectively sulfated poly-amido-saccharides are prepared by the polymerization of protected glucose b-lactams, followed by post-polymerization modification reactions. All polymers are water soluble, non-cytotoxic, and adopt helical conformations. I evaluated the anticoagulant activity of the sulfated polymers using in vitro, ex vivo, and in vivo methods as well as determined the mechanism of anticoagulation by amidolytic activity inhibition assays. Additionally, I synthesized new block copolymers as block copolymers are used for various applications including latex paints and pressure sensitive adhesives. Specifically, carbohydrate-based amphiphilic polymers are of interest for drug delivery applications, due to favorable properties such as cytocompatibility, low immunogenicity, and longer circulation time. We prepared PAS-based amphiphilic block polymers with varied polymer length, hydrophobic to hydrophilic ratio, and stereochemistry of hydrophilic component. I characterized these amphiphilic polymers by NMR, IR, GPC, DSC, TGA and CD, and they self-assemble in water to form nanostructures as determined by DLS, SEM, and cryo-TEM, and are non-cytotoxic. / 2024-11-16T00:00:00Z

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Thesis advisor: Jia Niu / Thesis advisor: Jim Morken / Polysaccharides make up one of the largest classes of nature’s macromolecules. However, they are severely understudied relative to other biomolecules such as proteins and DNA sequences. This is because discrete polysaccharides are difficult to isolate from nature or synthesize in laboratories in large enough quantities for thorough research. Polymerization is an efficient route to polysaccharides, yet has historically suffered from harsh conditions and lack of control. Herein, we investigate recent developments in the field of living polymerization as strategies towards synthesis of precision polysaccharides from 1,2- anhydrosugars. We specifically focus on cationic ring opening polymerization (ROP) and reversible addition-fragmentation chain transfer (RAFT) ROP polymerization of 1,2-O-Bn-3,4,6-anhydromannose and 1,2-O-Bn-3,4,6-anhydroglucose. Our research screens various catalyst/initiating systems. Our findings demonstrate that cationic ROP and RAFT polymerization are unsuccessful in the living ROP of 1,2-anhydrosugars. / Thesis (MS) — Boston College, 2023. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Cardiovascular disease is the leading cause of death in firefighters (FF) around the nation. Recent observational studies have emerged suggesting that FF consume calorically dense foods, high in sugar and fat, but low in nutritional value which can exacerbate heart diseases and impair performance. The potential to improve cardiometabolic and performance measurements when following a carbohydrate (CHO) restricted diet (CRD) has gained interest in the literature. To date, only one study has employed a nutrition intervention in FF, yet its’ focus was on nutrient dense foods and antioxidant supplements. Therefore, the purpose of this study was to examine the cardiometabolic and performance effects of a 28-day CRD in FF. 15 career FF participated and finished the present study. Participants reported to the laboratory on 9 separate occasions. Trial 1 consisted of participants having a blood draw performed for assessment of their heart disease risk followed by body composition, blood pressure, and a glucose challenge test (GCT) to assess glucose impairment following ingestion of a 75 g glucose beverage. Trial 2 consisted of a graded exercise cycling test with 5 stages followed by a maximal Wingate for 30 s. Finally, the last trial included the FF physical performance assessment (FPPA) which consisted of a 2.41-km run followed by 2 min of maximal pull-ups, push-ups, and sit-ups. The first 3 trials were used as familiarizations, the second 3 trials were used as baseline measurements, and the last 3 trials followed the 28-day CRD. The CRD consisted of ad-libitum consumption of fat and protein and keeping CHO < 25% daily kilocalorie intake. Dependent variables measured pre- and post-diet included body composition, lipid profile, insulin, cortisol, c-reactive protein (CRP), GCT, substrate oxidation rates, Wingate variables, and the FPPA. Following the diet, participants had significant reductions in CRP, blood pressure, 2.41-km run time, CHO oxidation rates, and fat mass. Participants also had significant increases in high density cholesterol count, fat oxidation rates, and pull-up repetitions. Overall, our results show that a CRD in a high-stress occupation can favorably change markers of heart disease and body composition without decrements to physical performance.

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