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Nanomaterials for Biological Applications: Drug Delivery and Bio- Sensing

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Nanomaterials for Biological Applications: Drug Delivery and Bio- Sensing University of New Orleans ScholarWorks@UNO University of New Orleans Theses and Dissertations Dissertations and Theses Spring 5-17-2013 Nanomaterials for Biological Applications: Drug Delivery and Bio- sensing Hui Ma [email protected] Follow this and additional works at: https://scholarworks.uno.edu/td Part of the Inorganic Chemistry Commons, Materials Chemistry Commons, and the Nanoscience and Nanotechnology Commons Recommended Citation Ma, Hui, "Nanomaterials for Biological Applications: Drug Delivery and Bio-sensing" (2013). University of New Orleans Theses and Dissertations. 1647. https://scholarworks.uno.edu/td/1647 This Dissertation is protected by copyright and/or related rights. It has been brought to you by ScholarWorks@UNO with permission from the rights-holder(s). You are free to use this Dissertation in any way that is permitted by the copyright and related rights legislation that applies to your use. For other uses you need to obtain permission from the rights-holder(s) directly, unless additional rights are indicated by a Creative Commons license in the record and/ or on the work itself. This Dissertation has been accepted for inclusion in University of New Orleans Theses and Dissertations by an authorized administrator of ScholarWorks@UNO. For more information, please contact [email protected]. Nanomaterials for Biological Applications: Drug Delivery and Bio-sensing A Dissertation Submitted to the Graduate Faculty of the University of New Orleans In partial fulfillment of the Requirements for the degree of Doctor of Philosophy in Chemistry by Hui Ma B.S. University of Science and Technology of China, 2007 M.S. University of New Orleans, 2010 May, 2013 Copyright 2013, Hui Ma ii ACKNOWLEDGEMENTS This research work was conducted at Department of Chemistry and Advanced Materials Research Institute (AMRI) at University of New Orleans (UNO), under the supervision of Professor Weilie Zhou. First, I would like to express my most sincere gratitude to my advisor Professor Zhou for recruiting me and providing consistent support through all the years of my study in his group. Thank to his disciplinary supervision, inspiring instruction and generous help, I’m able to successfully finish my work in time. I really enjoyed doing my work in his group, and I could not have imagined having a better advisor for my graduate study. I want to thank my committee members: Prof. O’Connor, Prof. Wiley, Prof. Cai and former committee member Prof. Poudeu. They shared a lot of valuable comments and suggestions with me on my projects and thesis. I want to thank our collaborators, Dr. Seth Pincus and Dr. Kejing Song from Children’s Hospital of New Orleans, Dr. Mark DeCoster form Louisiana Tech University, and Dr. Jost Geottert and Dr. Yoonyoung Jin from Louisiana State University, for their brilliant input for my projects and unreserved help with the instrumentation. I also want to thank many of my group members and friends: Dr. Jiajun Chen, Dr. Hongtao Yu, Miss. Jie Zhou, Miss. Sarah Wozny, Mr. Haiqiao Su and Mr. Satish Rai. They help me and support me during my Ph.D. studies. I’m indebted to Dr. Zhongming Zeng for him being incredibly patient and informative while training me for e-beam lithography. I also want to thank Dr. Kun Yao for many helpful discussions about the property of field effect transistor, and Dr. Kai Wang and Dr. Baobao Cao for their assistant in nanowire synthesis and electron microscopy. I gratefully acknowledge the support of this work by a research grant from Louisiana Board of Regents Contract No. LEQSF(2007-12)-ENH-PKSFI-PRS-04. Last, I want thank my family: my husband Haiou for his understanding and support. Without him, I cannot finish this work. I want to show my deepest appreciation to my parents Ruichang Ma and Junrui Dong who gave birth to me, raised me and support me for the last twenty-eight years. iii Table of Contents List of Schemes ............................................................................................................................ viii List of Figures ................................................................................................................................ ix List of Tables ................................................................................................................................ xiv Abstract ..........................................................................................................................................xv Part One: Magnetic Hollow Mesoporous Silica nanostructures for bio-medicine application Chapter I: Introduction 1 1.1 Synthesis of uniform mesoporous silica nanoparticles (MSN)..................................................2 1.2 Synthesis of hollow mesoporous silica nanoparticles (HMSN) ................................................4 1.2.1 Hard template method for synthesizing HMSN ..................................................................4 1.2.2 Soft template method for synthesizing HMSN ....................................................................6 1.2.3 Selective etching for synthesizing HMSN ...........................................................................7 1.3 Introducing superparamagnetic iron oxide nanoparticles (SPION) to mesoporous silica nanoparticle (MSN) ........................................................................................................................8 1.3.1 SPION/MSN core/shell structure .........................................................................................9 1.3.2 SPION embedded in MSN framework ..............................................................................10 1.3.3 Rattle type SPION core in MSN shell ............................................................................... 11 1.4 Further functionalization and applications of SPION/MSN ...................................................12 1.4.1 Drug/gene delivery.............................................................................................................13 1.4.2 Fluorescence imaging ........................................................................................................15 1.5 References ................................................................................................................................16 Chapter II: Magnetic porous hollow silica nanostructures from CaCO3 template for drug delivery application 21 2.1 Introduction ..............................................................................................................................21 2.2 Experimental ............................................................................................................................23 2.3 Result and discussion ...............................................................................................................28 2.3.1 Preparation of Fe3O4/CaCO3 composite nanoparticle templates ......................................29 iv 2.3.2 Synthesis of Magnetic Porous Hollow Silica Nanospheres (MPHSNs) and BET analysis.30 2.3.3 Synthesis of Magnetic Porous Hollow Silica Nanotubes (MPHSNTs) and BET analysis.33 2.3.4 Magnetic measurements. ...................................................................................................37 2.3.5 Drug loading and releasing. ..............................................................................................38 2.3.6 Toxicity study. ...................................................................................................................41 2.4 Conclusion ...............................................................................................................................43 2.5 References ................................................................................................................................44 Chapter III: Magnetic porous hollow silica nanospheres (MPHSNs) templated from polystyrene beads 46 3.1 Introduction ..............................................................................................................................46 3.2 Experimental ............................................................................................................................47 3.3 Result and discussion: ..............................................................................................................52 3.3.1 PS nanoparticle synthesis with acrylic acid as comonomer. ..............................................53 3.3.2 Synthesis of amine-ended Fe3O4 nanoparticles, linkage to carboxyl-ended PS beads and formation of magnetic porous hollow silica nanospheres (MPHSNs) .................................58 3.3.3 In-situ growth of Fe3O4 nanoparticles on PS particles.......................................................60 3.3.4 Preparation of mesoporous silica nanospheres based on PS templating. ...........................61 3.3.4.1 Ethanol-only medium for silica coating on PS nanoparticle. ......................................63 3.3.4.2 Water/ethanol mixed medium for silica coating on PS nanoparticles..........................66 3.3.5 Microemulsion method using PVP as stabilizer for preparation of PS beads with large yield....................................................................................................................................67 3.3.6 Mesoporous silica coating on PS nanoparticles. ................................................................69 3.3.7 In-situ growth of Fe3O4 nanoparticles on mesoporous silica nanospheres, synthesis and XRD study .........................................................................................................................71
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