M13 bacteriophage-enabled assembly of nanocomposites : synthesis and application in energy conversion devices

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Materials Science and Engineering, 2013.This electronic version was submitted by the student author. The certified thesis is available in the Institute Archives and Special Collections.Cataloged from student-submitted PDF version of thesis.Includes bibliographical references (p. 206-217).Lack of energy supply and non-uniform distribution of traditional energy sources, such as coal, oil, and natural gas, have brought up tremendous social issues. To solve these issues, highly efficient energy conversion devices including solar cells, water splitting cells, and lithium-ion batteries are required. In this thesis, by utilizing the biological scaffolds of M13 bacteriophage, nanocomposites with novel nanostructures and various functional nanomaterials have been synthesized, assembled, and fabricated into devices. Using excellent properties from each functional material in the nanocomposites, performance of the energy conversion devices has been improved. Specifically, in dye-sensitized solar cells, the electron collection efficiency is improved by the complex of the viruses and single-walled carbon nanotubes. The light harvesting efficiency is also improved by localized surface plasmon-enhanced photo-absorption of dye-molecules, with and without adding viruses into the titania photoanodes of dye-sensitized solar cells. In addition, virus-graphene complex is utilized to enhance the performance of lithium-ion batteries, by increasing the electron conductivity throughout the cathode active materials. Moreover, two types of virus-templated perovskite ternary metal oxide materials (strontium titanate and bismuth ferrite) are synthesized and demonstrated for photocatalytic and photovoltaic properties.by Xiangnan Dang.Ph.D

Layer-by-layer assembled fluorescent probes in the second near-infrared window for systemic delivery and detection of ovarian cancer

Fluorescence imaging in the second near-infrared window (NIR-II, 1,000–1,700 nm) features deep tissue penetration, reduced tissue scattering, and diminishing tissue autofluorescence. Here, NIR-II fluorescent probes, including down-conversion nanoparticles, quantum dots, single-walled carbon nanotubes, and organic dyes, are constructed into biocompatible nanoparticles using the layer-by-layer (LbL) platform due to its modular and versatile nature. The LbL platform has previously been demonstrated to enable incorporation of diagnostic agents, drugs, and nucleic acids such as siRNA while providing enhanced blood plasma half-life and tumor targeting. This work carries out head-to-head comparisons of currently available NIR-II probes with identical LbL coatings with regard to their biodistribution, pharmacokinetics, and toxicities. Overall, rare-earth-based down-conversion nanoparticles demonstrate optimal biological and optical performance and are evaluated as a diagnostic probe for high-grade serous ovarian cancer, typically diagnosed at late stage. Successful detection of orthotopic ovarian tumors is achieved by in vivo NIR-II imaging and confirmed by ex vivo microscopic imaging. Collectively, these results indicate that LbL-based NIR-II probes can serve as a promising theranostic platform to effectively and noninvasively monitor the progression and treatment of serous ovarian cancer.United States. Department of Defense. Ovarian Cancer Research Program (TEAL Innovator Award OC120504)National Cancer Institute (U.S.) (Center for Cancer Nanotechnology Excellence Grant 5-U54- CA151884-03

Tunable Localized Surface Plasmon-Enabled Broadband Light-Harvesting Enhancement for High-Efficiency Panchromatic Dye-Sensitized Solar Cells

In photovoltaic devices, light harvesting (LH) and carrier collection have opposite relations with the thickness of the photoactive layer, which imposes a fundamental compromise for the power conversion efficiency (PCE). Unbalanced LH at different wavelengths further reduces the achievable PCE. Here, we report a novel approach to broadband balanced LH and panchromatic solar energy conversion using multiple-core–shell structured oxide-metal-oxide plasmonic nanoparticles. These nanoparticles feature tunable localized surface plasmon resonance frequencies and the required thermal stability during device fabrication. By simply blending the plasmonic nanoparticles with available photoactive materials, the broadband LH of practical photovoltaic devices can be significantly enhanced. We demonstrate a panchromatic dye-sensitized solar cell with an increased PCE from 8.3% to 10.8%, mainly through plasmon-enhanced photoabsorption in the otherwise less harvested region of solar spectrum. This general and simple strategy also highlights easy fabrication, and may benefit solar cells using other photoabsorbers or other types of solar-harvesting devices.Eni-MIT Energy Initiative Founding Member ProgramNational Science Foundation (U.S.) (ECCS Award 1028568)United States. Air Force Office of Scientific Research (AFOSR MURI Award FA9550-12-1-0488

Graphene Sheets Stabilized on Genetically Engineered M13 Viral Templates as Conducting Frameworks for Hybrid Energy-Storage Materials

Utilization of the material-specific peptide–substrate interactions of M13 virus broadens colloidal stability window of graphene. The homogeneous distribution of graphene is maintained in weak acids and increased ionic strengths by complexing with virus. This graphene/virus conducting template is utilized in the synthesis of energy-storage materials to increase the conductivity of the composite electrode. Successful formation of the hybrid biological template is demonstrated by the mineralization of bismuth oxyfluoride as a cathode material for lithium-ion batteries, with increased loading and improved electronic conductivity.National Institute for International Education (Korea) (Korean Government Scholarship Program)United States. Army Research Office (Institute for Collaborative Biotechnologies (ICB))National Institutes of Health (U.S.) (Materials Research Science and Engineering Centers program

Deep-tissue optical imaging of near cellular-sized features

Detection of biological features at the cellular level with sufcient sensitivity in complex tissue remains a major challenge. To appreciate this challenge, this would require fnding tens to hundreds of cells (a 0.1 mm tumor has ~125 cells), out of ~37 trillion cells in the human body. Near-infrared optical imaging holds promise for high-resolution, deep-tissue imaging, but is limited by autofuorescence and scattering. To date, the maximum reported depth using second-window near-infrared (NIR-II: 1000–1700 nm) fuorophores is 3.2 cm through tissue. Here, we design an NIR-II imaging system, “Detection of Optically Luminescent Probes using Hyperspectral and difuse Imaging in Near-infrared” (DOLPHIN), that resolves these challenges. DOLPHIN achieves the following: (i) resolution of probes through up to 8 cm of tissue phantom; (ii) identifcation of spectral and scattering signatures of tissues without a priori knowledge of background or autofuorescence; and (iii) 3D reconstruction of live whole animals. Notably, we demonstrate noninvasive real-time tracking of a 0.1 mm-sized fuorophore through the gastrointestinal tract of a living mouse, which is beyond the detection limit of current imaging modalities.Untied States. National Cancer Institute. Cancer Center Support (Grant P30-CA14051)United States. National Cancer Institute. Center for Cancer Nanotechnology Excellence (Grant 5-U54-CA151884-03

Layer-by-layer assembled fluorescent probes in the second near-infrared window for systemic delivery and detection of ovarian cancer

Fluorescence imaging in the second near-infrared window (NIR-II, 1,000–1,700 nm) features deep tissue penetration, reduced tissue scattering, and diminishing tissue autofluorescence. Here, NIR-II fluorescent probes, including down-conversion nanoparticles, quantum dots, single-walled carbon nanotubes, and organic dyes, are constructed into biocompatible nanoparticles using the layer-by-layer (LbL) platform due to its modular and versatile nature. The LbL platform has previously been demonstrated to enable incorporation of diagnostic agents, drugs, and nucleic acids such as siRNA while providing enhanced blood plasma half-life and tumor targeting. This work carries out head-to-head comparisons of currently available NIR-II probes with identical LbL coatings with regard to their biodistribution, pharmacokinetics, and toxicities. Overall, rare-earth-based down-conversion nanoparticles demonstrate optimal biological and optical performance and are evaluated as a diagnostic probe for high-grade serous ovarian cancer, typically diagnosed at late stage. Successful detection of orthotopic ovarian tumors is achieved by in vivo NIR-II imaging and confirmed by ex vivo microscopic imaging. Collectively, these results indicate that LbL-based NIR-II probes can serve as a promising theranostic platform to effectively and noninvasively monitor the progression and treatment of serous ovarian cancer.United States. Department of Defense. Ovarian Cancer Research Program (TEAL Innovator Award OC120504)National Cancer Institute (U.S.) (Center for Cancer Nanotechnology Excellence Grant 5-U54- CA151884-03

M13 Virus-Enabled Synthesis of Titanium Dioxide Nanowires for Tunable Mesoporous Semiconducting Networks

Mesoporous semiconducting networks exhibit advantageous photoelectrochemical properties. The M13 virus is a versatile biological scaffold that has been genetically engineered to organize various materials into nanowire (NW)-based mesoporous structures. In this study, high-aspect ratio titanium dioxide NWs are synthesized by utilizing M13 viruses as templates, and the NWs are assembled into semiconducting mesoporous networks with tunable structural properties. To understand the effects of different morphologies on the photovoltaic performance, the as-fabricated networks are employed as photoanodes in liquid-state dye-sensitized solar cells (DSCs). Compared with traditional nanoparticle-based photoanodes, the NW-based DSC photoanodes demonstrate much higher electron diffusion lengths while maintaining a comparable light harvesting capacity, thus leading to improved power conversion efficiencies. In addition, the NW-based semiconducting mesoporous thin films are able to load sufficient organolead iodide perovskite materials into the interconnected pores, and the perovskite-coated films are utilized as efficient photoanodes for solid-state organolead iodide perovskite hybrid solar cells and achieve power conversion efficiencies superior to those of liquid-state DSCs.Eni S.p.A. (Firm) (Eni-MIT Energy Fellowship)Natural Sciences and Engineering Research Council of Canada (Postgraduate Scholarship

Using Clinical Scales and Digital Measures to Explore Falls in Patients with Lewy Body Dementia

Introduction: PRESENCE was a phase 2 clinical trial assessing the efficacy of mevidalen, a D1 receptor positive allosteric modulator, for symptomatic treatment of Lewy body dementia (LBD). Mevidalen demonstrated improvements in motor and non-motor features of LBD, global functioning, and actigraphy-measured activity and daytime sleep. Adverse events (AEs) of fall were numerically increased in mevidalen-treated participants. Methods: A subset of PRESENCE participants wore a wrist actigraphy device for 2-week periods pre-, during, and posttreatment. Actigraphy sleep and activity measures were derived per period and analyzed to assess for their association with participants’ reports of an AE of fall. Prespecified baseline and treatment-emergent clinical characteristics were also included in the retrospective analysis of falls. Independent-samples t test and χ2 test were performed to compare the means and proportions between individuals with/without falls. Results: A trend toward more falls was observed with mevidalen treatment (31/258 mevidalen-treated vs. 4/86 in placebo-treated participants: p = 0.12). Higher body mass index (BMI) (p < 0.05), more severe disease measured by baseline Movement Disorder Society-Unified Parkinson’s Disease Rating Scale (MDS-UPDRS) part II (p < 0.05), and a trend toward improved Alzheimer’s Disease Assessment Scale-Cognitive Subscale 13 (ADAS-Cog13) (p = 0.06) were associated with individuals with falls. No statistically significant associations with falls and treatment-emergent changes were observed. Conclusion: The association of falls with worse baseline disease severity and higher BMI and overall trend toward improvements on cognitive and motor scales suggest that falls in PRESENCE may be related to increased activity in mevidalen-treated participants at greater risk for falling. Future studies to confirm this hypothesis using fall diaries and digital assessments are necessary

Data from: Deep-tissue optical imaging of near cellular-sized features

Detection of biological features at the cellular level with sufficient sensitivity in complex tissue remains a major challenge. To appreciate this challenge, this would require finding tens to hundreds of cells (a 0.1 mm tumor has ~125 cells), out of ~37 trillion cells in the human body. Near-infrared optical imaging holds promise for high-resolution, deep-tissue imaging, but is limited by autofluorescence and scattering. To date, the maximum reported depth using second-window near-infrared (NIR-II: 1000–1700 nm) fluorophores is 3.2 cm through tissue. Here, we design an NIR-II imaging system, “Detection of Optically Luminescent Probes using Hyperspectral and diffuse Imaging in Near-infrared” (DOLPHIN), that resolves these challenges. DOLPHIN achieves the following: (i) resolution of probes through up to 8 cm of tissue phantom; (ii) identification of spectral and scattering signatures of tissues without a priori knowledge of background or autofluorescence; and (iii) 3D reconstruction of live whole animals. Notably, we demonstrate noninvasive real-time tracking of a 0.1 mm-sized fluorophore through the gastrointestinal tract of a living mouse, which is beyond the detection limit of current imaging modalities