Reactive oxygen species (ROS) are byproducts of physiological processes in human body, and strengthened production of ROS is known to cause acute conditions such as inflammation, aging, Alzheimer's disease, melanoma and ovarian cancer, fibrosis and multiple sclerosis. Therefore, early detection of ROS at nanomolar concentration (at cellular level) and developing more potent antioxidants is essential for regular health monitoring. As an example, ROS are also responsible for inflammation reactions at orthopedic implants-tissue interface triggered by wear debris. Inflammation induced by ROS results in revision surgery. Coatings of redox-active materials exhibiting antioxidant properties on implants have potential to mitigate the inflammation and delay the need of revision surgery. This dissertation focus on developing advanced functional nanomaterials by tailoring the surface chemistry of existing materials. Surface chemistry of materials can be altered by introducing surface and edge defects in the lattice structure Three materials system doped cerium oxide nanoparticles (d-CNPs), cerium oxide thin films (CeOx) and molybdenum disulfide (MoS2) nanoparticles, have been studied for its surface and edge contributions in potential biomedical and biosensing applications. Surface (d-CNPs and CeOx thin films) and edge chemistry (MoS2) have been tailored to understand its role and specific response. Surface Ce3+/Ce4+ oxidation state in CNPs controls the bio-catalytic activity. Higher superoxide dismutase (SOD) is demonstrated by high Ce3+/Ce4+ oxidation state. On the other hand, improved catalase mimetic activity is observed for low Ce3+/Ce4+ CNPs. Different CNPs preparation results in different Ce3+ to Ce4+ ratio, particle size, surface coating, and agglomeration, thus significantly varying the antioxidant properties of CNPs. In the first section of the dissertation, sustainable one-step room temperature synthesis of rare earth element (La, Sm, and Er) d-CNPs have been developed to effectively control the Ce3+ to Ce4+ ratio for specific biological application. Substitution of Ce4+ ions by trivalent dopants from ceria lattice increases the oxygen vacancies and density of catalytic sites. Uniform distribution of trivalent dopant in ceria lattice confirmed by EFTEM is attributed to enhanced SOD mimetic activity, ROS scavenging and tuning surface Ce3+/Ce4+ oxidation state in CNPs. Surface chemistry of redox-active cerium oxide coating on orthopedic implants also plays a vital role in scavenging ROS and mitigating inflammation. Thus, surface chemistry of CeOx thin films deposited by atomic layer deposited (ALD), have also been tailored by controlling the film thickness. CeOx film of 2 nm thickness has high Ce3+/Ce4+ (ratio 1) whereas higher thickness films (6-33 nm) have lower Ce3+/Ce4+ (ratio 0.30-0.37). These films have been further tested for catalase mimetic activity and hydrogen peroxide (H2O2) detection. Sensor selectivity is always a key issue. Most often, ascorbic acid found in the biological system, interfere in the electrochemical detection of H2O2 resulting in selectivity issue, thus protective Nafion layer is required to prevent cerium oxide-ascorbic acid interaction. To improve the selectivity of electrochemical sensors, Sulfur-deficient redox-active MoS2 have been utilized for electrochemical detection of pharmaceutically relevant chemical species. S-deficient MoS2 nanoparticles have been prepared by liquid exfoliation method to increase Mo-edge density and tested as sensing materials for detection of pharmaceutically relevant H2O2, hypochlorous acid (HOCl) and reactive nitrogen (NO*) species. The addition of ascorbic acid and uric acid have shown no interference during H2O2 detection. Change in S to Mo ratio have been studied using x-ray photoelectron spectroscopy. Density functional theory (DFT) have been employed to understand the detection mechanism and size-dependent sensitivity of MoS2. DFT study further reveals the role of S-deficiency and Mo- and S-edges in the higher catalytic activity of 5-7 nm MoS2 particles. Through these studies, the importance of defects in nanomaterials and their exotic properties at the nanoscale have been demonstrated. Understanding developed from these studies have provided the framework to develop more advanced functional nanomaterials for biomedical and biosensing applications.


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Graduation Date





Seal, Sudipta


Doctor of Philosophy (Ph.D.)


College of Engineering and Computer Science


Materials Science Engineering

Degree Program

Materials Science and Engineering









Release Date

November 2020

Length of Campus-only Access

3 years

Access Status

Doctoral Dissertation (Open Access)