The modification of materials and surfaces with fluorocarbons enables ultralow surface energies in the development of numerous applications of cutting-edge science and technology. The use of partially fluorinated materials offers advantages in terms of cost and synthetic flexibility, and in some cases, performance, when compared to allfluorocarbon materials. This research employs a surface-initiated polymerization (SIP), namely surface-initiated ring-opening metathesis polymerization (SI-ROMP), to grow partially fluorinated coatings with critical surface tensions as low as 9 mN/m that establish new standards in thickness with tremendous control over microscale surface texturing. SIP techniques provide robust chemisorption, diverse chemical functionality, control over film growth, and the ability to uniformly coat planar and non-planar surfaces. Although SIP methods have been previously used to deposit partially fluorinated films, the ability to grow such films with thicknesses above a few micrometers, with controlled textures, or within nanoporous materials has not been demonstrated prior to this work. Accordingly, this dissertation focuses on: (1) the fabrication and characterization of novel partially fluorinated/inorganic composites by employing SI-ROMP within nanoporous architectures to create membranes with tunable wettability and ion transport; (2) the amplification of the SIP of partially fluorinated polymer films to fabricate specialty coatings that yield thicknesses from 4 12 µm in as little as 15 min of polymerization. Remarkably, these films exhibit resistance against ion transport in excess of 10 GΩcm^2, which is the highest value ever reported for SIP films; and the development of a new SIP-based approach to (3) fabricate microscale surface features with height modulation and to (4) reproduce the complex surface topographies of superhydrophobic natural surfaces onto solid supports. This process enables the preparation of microtextured films and novel biomimetic coatings that reproduce superhydrophobic plant leaves, and could radically impact applications such as self-cleaning surfaces and chemical- and corrosion-resistant coatings.

<p> This industrial project is designed to develop a chemical process for the formulation of liquid soap. Three ingredients required to make liquid soap are rainwater, oil, and potassium hydroxide. These three ingredients, when mixed to exhibit a chemical reaction, generate the saponification reaction and can produce soap and byproduct glycerol. The liquid soap is made from indigenous materials including coconut oil, palm oil, rainwater, cinnamon hydrosol, and potassium hydroxide extracted from wood ash as well as commercially available materials including potassium hydroxide.</p><p> The Fourier Transfer Infrared Spectroscopy (FTIR) measures the functional groups, while the surface tension measures the critical micelle concentration; both instruments measure the standard Sodium Dodecyl Sulfate (SDS). The SDS results are then compared to oils, soap products, and byproduct glycerol. These measurements are made to determine the effectiveness of soap and to compare the wood ash potassium hydroxide with commercially available potassium hydroxide in the soap products.</p>

Cancer is the second leading cause of death globally according to the World Health Organization. Aggressive cancers that have genetic mutations for surface receptors require more versatile and multifunctional treatments. Plasmonic nanostructures have emerged as novel platforms for the management and mitigation of cancer due to their high biocompatibility, ease of bioconjugation, tunability of resonance to tissue penetrating wavelengths, and ability to convert light to heat for photothermal ablation. In this work, we synthesized multibranched gold nanoantennas (MGNs) via HEPES-mediated growth method and investigated their performance in delivering simultaneous diagnostic and therapeutic (theranostic) components in cancer models. Due to the presence of multiple sharp protrusions, MGNs demonstrated a refractive index sensitivity of 373 nm/RIU, as well as, intense photothermal efficiencies, rising the temperature of surrounding medium to ~54 °C within 5 minutes of laser illumination. Additionally, MGN-substrates were manufactured for point of care diagnostic (POCD) systems utilizing surface enhanced Raman spectroscopy (SERS). MGN-paper was used to obtain a detection limit of 100 fM of human serum albumin (HSA) complexed with indocyanine green (ICG). Further, by incorporating protein detection via SERS tag technology, we designed a sandwich architecture using MGN-glass for prostate specific antigen (PSA) biomarker sensing. Lastly, we showed the theranostic capability of MGNs in triple negative breast cancer (TNBC) both in vitro and in vivo via human xenografts. Utilizing the light to heat conversion capacities of the MGNs, actively targeted photothermal therapy was demonstrated in EGFR overexpressing MDA MB 231 cells, with no observable off-site toxicities. Lastly, using SERS imaging, we targeted the epidermal growth factor receptor (EGFR) and immune checkpoint receptor, programmed death ligand 1 (PD-L1), and acquired 2-dimensional SERS âtraffic mapsâ of the 231 cells. In addition, a blocking study in vivo revealed ~30 % decrease in SERS signal when receptor sites were occupied, verifying the active targeting properties of the antibody coated MGNs. This encompassed work demonstrates the adaptable potential of the synthesized theranostic MGNs to provide predictive, personalized, and image-guided therapies, facilitating the transition to individualized cancer medicine.

Process monitoring is required for safety of operations, considerable reduction in downtime, and decrease in manufacturing costs. Chemical Engineers have a high responsibility in the proper functioning of a process plant as any deviations from normal operations might lead to a disastrous effect in loss of lives and infrastructure. The increased number of microprocessors due to the reduction in cost (Effect of Moores Law) has increased the speed of computers. This has led to the increase in the amount of data storage. Thus, creating a scope for us to train machines to identify representations of the data. Data clustering, an exploratory data analytics technique helps us in the process of unsupervised learning: unclassified datasets. Previously, process monitoring has been done using statistical techniques such as component analyses, however one of the challenge in practical applications is the difficulty to classify (cluster) the information from a high dimension data set commonly encountered in chemical process industry. There are many clustering algorithms such as K-Means, Mean Shift, Hierarchical, DBSCAN. In this study a detailed analysis of the alternative approaches for data classification was performed including conventional and novel techniques arising from Computer Science. This is the first reported instance of the use of HDBSCAN, a hybrid of Hierarchical and Density Based Spatial Clustering with Applications and noise, in a chemical process data. We have concluded that HDBSCAN outperforms the other clustering algorithms on chemical process dataset. The Chemical process dataset used was from the Tennessee Eastman Process. Since, in this study we compared clustering algorithms we realized the need for an easy automation for running clustering algorithms ,hence we built an application called Mi ClustoRoma, a graphical user interface built on python for classifying and visualizing chemical process datasets.

Since their commercial debut in 1991, Li-ion batteries (LIBs) have revolutionized the functionality of portable electronic devices, and the LIB industry continues to grow today due emerging applications such as electric vehicle propulsion. Despite the extraordinary success of LIBs, many devices are still limited by battery performance, and thus new batteries with higher energy density, faster rechargeability, and longer cycle life must be developed to satisfy the ever-increasing demands of consumers. This dissertation details the fabrication and characterization of electrospun particle/polymer fiber mats as LIB electrodes, including: (i) anodes containing titania nanoparticles, carbon powder, and poly(acrylic acid) (TiO2/C/PAA), (ii) anodes containing carbon powder and poly(vinylidene fluoride) (C/PVDF), (iii) anodes containing Si nanoparticles, carbon powder, and PAA (Si/C/PAA), and (iv) cathodes containing LiCoO2 nanoparticles, carbon powder, and PVDF (LiCoO2/C/PVDF). The composition, thickness, fiber volume fraction, and fiber interconnectivity of electrospun mats can be easily controlled to achieve high capacities at fast charge/discharge rates. An electrospun TiO2/C/PAA anode with a thickness of 600 µm had an areal capacity of 0.97 mAh cm-2 at 2C which is much greater than that of a slurry cast anode of the same composition and loading (0.53 mAh cm-2). Likewise, a C/PVDF anode with a fiber volume fraction of 0.85 had a high volumetric capacity of 55 mAh cm-3 at 2C compared to only 27 mAh cm-3 for a conventional slurry cast graphite anode. Si/C/PAA fiber mat anodes had extremely high gravimetric, areal, and volumetric capacities of 1,484 mAh g-1, 4.5 mAh cm-2, and 750 mAh cm-3, respectively. C/LiCoO2 and Si/LiCoO2 full cells prepared with an electrospun anode and electrospun cathode had high specific energy densities of 150 and 270 Wh kg-1, respectively, which are among the highest values reported in the literature to date. The excellent performance of electrospun particle/polymer fiber mat electrodes is attributed to their: (i) large electrode/electrolyte interfacial areas, (ii) short Li+ transport pathways, and (iii) good electrolyte infiltration throughout the intra- and interfiber void space of the mats. These results demonstrate that the intelligent organization of electroactive powders into fiber mat electrodes can enhance Li+ transport rates and improve LIB performance.

Wastewater reuse is considered globally as a very important element of sustainable water management. Conventional wastewater treatment methods are not effective for the degradation of toxic trace organic compounds, so advanced treatment processes are sometimes needed when the wastewater effluent is likely to be reused or discharged to a river. The existence of toxic trace organic contaminants in the effluent wastewaters has increased awareness of environmental effects and potential concerns for human health. In this work, the advanced oxidation process (AOP) under solar irradiation was successfully used to decompose p-cresol, which is considered to be a toxic trace organic contaminant, from wastewater effluents. The objective of this thesis was to investigate the effect of the EfOM on the overall degradation of the trace organic matter and bulk organic matter through the formation of reactive oxygen species (ROS) and photoexcited dissolved organic matter intermediates (DOM*) under sunlight irradiation. Solar photolysis experiments were conducted to determine the degradation of p-cresol at different conditions, including varying the secondary effluent WW concentration, the initial concentration of the target compound and light intensity. Results from these experiments were reported and discussed to get the optimal treatment processes.

No description available.

Higher oxygenates synthesis by catalytic conversion of synthesis gas are the potential approaches to replace fossil fuels and produce chemicals for pharmaceutical manufacture, detergents and polymer industry. Cobalt-based catalysts are the most promising catalysts to replace noble metal catalysts for producing ethanol, acetaldehyde and higher oxygenates via CO hydrogenation. The formation of higher oxygenates requires active sites that can adsorb CO non-dissociatively and insert to the alkyl intermediate. The hydrogenation of the CO-inserted intermediates yields C2 and C2+ oxygenates. The main focus of this study is to investigate the active site for non-dissociative CO adsorption, and the modification of the catalysts to enhance the production rate for higher oxygenates. The effect of different structural promoters are investigated on copper-cobalt catalysts. Three cobaltcopper catalysts singly promoted with La, Zr, or Al were studied for catalytic conversion of syngas to higher alcohols. CO hydrogenation was carried out, and catalyst activity and selectivity to higher alcohols are the greatest on La promoted catalyst. La promoted catalyst differs from the other two in the first 10 h of time-on-stream, with the product distribution shifted to favor oxygenates formation. These results suggest changes on La promoted catalyst during the reaction. The DRIFTS study of CO adsorption behavior on La promoted copper-cobalt catalyst observed that CO linearly adsorbed on Co2C site. A cobalt carbide phase was formed in the reaction, and Co2C is able to adsorb CO associatively and insert to the intermediates. X-ray absorption techniques detected the existence of cobalt carbide in the lanthanum promoted cobalt-copper catalysts. A further reaction study on a promoter-free bulk Co2C catalyst also detected higher oxygenates as products. To improve the selectivity to ethanol and higher oxygenates and provide a stable catalyst for CO hydrogenation, a novel method using metal organic framework as precursors was performed to synthesize a series of potassium-promoted cobalt catalysts for higher oxygenates synthesis. The MOF-mediated synthesis method provide the catalyst with superior resistance to sintering and deactivation. The potassium promoters suppresses the formation of methane and higher hydrocarbons, while cobalt carbide is formed from the metallic cobalt and the carbon in the catalyst. As a result, the potassium-promoted catalyst synthesized by MOF-mediated method gives high yields to ethanol and higher oxygenates. CO hydrogenation was also carried out using real biomass-derived syngas. The low CO composition and high CO/H2 ratio in the biomass-derived syngas require special catalysts to carry out Fischer-Tropsch reaction and produce liquid fuels. By using K-promoted iron catalysts and ruthenium catalysts, along with the addition of steam into the syngas feedstock, a high yield of liquid hydrocarbons were achieved in the reaction. This study shed light on using biomass-derived syngas for the production of higher oxygenates.

Thesis: Ph. D., Massachusetts Institute of Technology, Department of Chemical Engineering, 2018 / Cataloged from PDF version of thesis. / Includes bibliographical references (pages 83-101). / Hydrogen peroxide (H₂O₂) is a well-known oxidant species commonly produced in eukaryotic organisms as a result of cellular metabolism that plays a central role in numerous processes in cells, and dysregulation of this species can result in a number of different disease states in human cells. In the case of cancer, elevated metabolism is believed to result in higher rates of H₂O₂ production in these cells, as well as more susceptibility to H₂O₂-induced apoptosis than normal cells. To this end, researchers have identified several therapeutic compounds that are believed to kill cancer cells via the intracellular elevation of one or more oxidants. However, due to the limitations of current tools for detection of these species, little is known about which therapeutic compounds induce toxicity via elevation of specific oxidants, which would aid in the identification of susceptible tumors to these treatments. / Currently, the main limitation of genetically-encoded tools for detection of H₂O₂ in these applications is the low sensitivity to H₂O₂ . Most genetically-encoded probes for this species used in human cells utilize H₂O₂-responsive domains with reaction rate coefficients nearly two orders of magnitude lower than other, more reactive peroxidases in the cell, such as peroxiredoxins (Prxs). In this regard, several studies have demonstrated that Prxs should react with the majority of intracellular H₂O₂ on the basis of a high reaction rate coefficient with H₂O₂ and intracellular abundance. In light of these studies, research in the field of redox biology has shifted to focus more on Prxs' role as natural sensors of H₂O₂ fluctuations in human cells. To this end, the first part of my thesis project focuses on the development of a genetically-encoded probe for H₂O₂-mediated human Prx2 oxidation in human cells. / The second part of my thesis focuses on the application of this probe in a high-throughput screen to identify small-molecule cancer therapeutics that act through H₂O₂-mediated mechanisms. Together, this thesis lays the foundation for a new class of genetically-encoded sensors that enable specific, sensitive measurement of H₂O₂ perturbations in human cells in response to redox-based therapeutics, which will facilitate the advancement of these therapeutic compounds in the future. / by Troy Frederick Langford. / Ph. D. / Ph.D. Massachusetts Institute of Technology, Department of Chemical Engineering

Thesis: Ph. D., Massachusetts Institute of Technology, Department of Chemical Engineering, 2018 / Cataloged from PDF version of thesis. / Includes bibliographical references (pages 180-199). / Messenger RNAs (mRNAs) are an emerging therapeutic modality that holds great promise to specifically and completely treat genetic disease. mRNA has been used as a vaccine, as a protein replacement therapy, and even as a means of inducing permanent genomic editing via CRISPR. However, unlike traditional small molecule drugs, naked mRNA cannot readily enter the cellular cytosol, where it must localize in order to be successfully translated. The field of nucleic acid delivery, therefore, is largely concerned with the development of materials which can encapsulate mRNA and facilitate its transport into cellular cytoplasm in vivo. Many lipid nanoparticles originally designed to deliver short interfering RNA (siRNA) have been successfully repurposed to deliver mRNA, although their application is limited mainly to the liver. Thus, there is a continued need for the development of new materials for mRNA delivery in order to expand its therapeutic potential throughout the body. / Another class of nucleic acid delivery materials, poly(P-amino ester)s, or PBAEs, have been successful in delivering DNA cargo in vitro and in vivo, but their capacity for mRNA delivery has been relatively understudied. In this thesis, we utilized formulation techniques developed for lipid nanoparticles to systemically deliver mRNA-loaded PBAEs. We showed that non-covalent formulation of PBAE-mRNA nanoparticles with a polyethylene glycol-lipid conjugate imparts serum stability to the nanoparticles, which in turn correlates with in vivo efficacy. Specifically, we demonstrated that these materials are mainly effective in lung tissue following intravenous administration. The lung targeting and potency of these nanoparticles was then greatly improved through statistical optimization of the polymer synthesis and nanoparticle formulation. These optimized nanoparticles transfected the majority of lung endothelial cells, as well as a variety of immune cells populations. / The nanoparticles were also used as a means of quantitatively comparing mRNA and DNA delivery in vitro and in vivo. We showed a drastic decrease in DNA potency in vivo compared to mRNA, attributed to the difficulty in crossing the nucleus of slowly dividing cells. Moreover, we observed similar kinetics of protein expression between mRNA and DNA. Additionally, we demonstrated in in vitro proof-of-concept studies that PBAE nanoparticles are capable of CRISPR-mediated genome editing. We also show successful mRNA delivery in a variety of other tissues beyond the lung endothelium. Through the development of novel chemistries using both PBAEs and lipids, we were able to achieve mRNA delivery specifically to the lung endothelium as well as the spleen in vivo. Taken together, the materials developed herein greatly expand the therapeutic capabilities of mRNA. / It is our hope that the work presented in this thesis translates into therapeutically relevant treatments while also providing insight into design criteria for successful mRNA delivery. / by James Cliff Kaczmarek. / Ph. D. / Ph.D. Massachusetts Institute of Technology, Department of Chemical Engineering