Nanostructured, electroactive and bioapplicable materials

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School of Biomedical Engineering, Science and Health Systems for collaborations in bioapplicable electroactive materials. I am grateful to many people for their selfless support in many areas. I especially acknowledge Mr. David von Rohr for his help in electron microscopics measurements, Dr. Jeffrey Honovich for mass spectral measurements, Dr. Guoliang Yang for AFM studies, Mr. Prithwiraj Maitra of Temple University for some TGA measurements, and Ms. Edith Smith for her kindly help and coordination in obtaining the chemicals and instruments for our research work. I thank Dr. Jigeng Xu, Dr. Hua Dong, Dr. Homayoun Jamasbi, Mr. Muduo Lin, Ms. Houping Yin, Mr. Zhengfei Sun, Ms. Kate Ong, Ms. Alpa Patel and Mr. Subhabrata Bhattacharyya, in Dr. Yen Wei’s group, either previously or currently. They have greatly enriched my experience at Drexel, and brought me many cherishable memories. I also want to thank the people in the Department of Chemistry, including all professors, staff and my fellow graduates, for providing such a joyful studying and working environment. I am grateful to my parents, Mr. and Mrs. Hai Cheng and Linmeng Wang, and my sister, Ms. Gung Cheng, for their continuous encouragement and unconditional love throughout. I shall be indebted to them forever. Finally, I want to thank my husband, Yunkai Zhou, who is now also a Ph.D. candidate majoring in computer networking -- “polymers of computers” as he always described. Discussion with him has always been amazingly helpful, even thought we are not in the same field. It is him always being there lighting my spirit up, keeping my heart warm, and showing me the sunshine on the road. iv
Table of Contents List of Tables.....................................................................................................................xii List of Figures ..................................................................................................................xiii Abstract ........................................................................................................................ xxi Preface ........................................................................................................................... 1 Chapter 1. An Overview to Nanostructured Porous Sol-Gel Materials.............................. 5 1.1. Introduction .......................................................................................................... 5 1.2. Fundamental Sol-Gel Process .............................................................................. 7 1.2.1. Inorganic Salt Precursors ............................................................................ 7 1.2.2. Alkoxide Precursors .................................................................................... 8 1.3. Mesoporous Materials from Surfactant Templated Sol-Gel Methods ................. 9 1.4. Mesoporous Materials from Nonsurfactant Templated Sol-Gel Methods......... 13 1.5. Characterization Methods for Porous Materials................................................. 15 1.5.1. Gas Sorption Measurement ....................................................................... 18 1.5.1.1. Classification of Adsorption Isotherms............................................ 18 1.5.1.2. Adsorption Hysteresis ...................................................................... 20 1.6. References .......................................................................................................... 21 Chapter 2. Mesoporous Sol-Gel Material Prepared Using Thermal Sensitive Templates: New Opportunities to Convenient Synthesis................................ 30 2.1. Introduction ........................................................................................................ 30 2.1.1. Surfactant Templates and Their Removal................................................. 31 2.1.2. Nonsurfactant Templates and Their Removal........................................... 34 2.1.3. Thermal Sensitive Templates.................................................................... 34 v
Page 1: Nanostructured, Electroactive and B
Page 4 and 5: Dedications This dissertation is de
Page 8 and 9: 2.2. Experimental .................
Page 10 and 11: 5.2.2. Treatment of Substrate Surfa
Page 12 and 13: 8.2. Electroactive, Bioapplicable M
Page 14 and 15: List of Tables Table 2-1. Compositi
Page 16 and 17: Figure 2-9. BJH pore size distribut
Page 18 and 19: xvi pattern of gold nanoparticles i
Page 20 and 21: xviii PANI under culturing conditio
Page 22 and 23: Figure B-8. Cyclic voltammogram (Pt
Page 24: The resultant polyaniline-collagen
Page 27 and 28: Chapter 2 presents a study focused
Page 29 and 30: Chapter 7 is focused on the synthes
Page 31 and 32: surfactant templated method was ext
Page 33 and 34: The porous structure of the silica
Page 35 and 36: Before early 1990s, with a pore or
Page 37 and 38: − Neutral surfactants: the hydrop
Page 39 and 40: The mechanism of nonsurfactant temp
Page 41 and 42: zero in a pore. Structural informat
Page 43 and 44: 1.5.1. Gas Sorption Measurement As
Page 45 and 46: which is usually associated with ca
Page 47 and 48: 16. Iler, R. K. The Chemistry of Si
Page 49 and 50: 52. Sayari, A.; Danumah, C.; Moudra
Page 51 and 52: Figure 1-1. Three structure types p
Page 53 and 54: Figure 1-3. IUPAC classification of
Page 55 and 56: Chapter 2. Mesoporous Sol-Gel Mater
Page 57 and 58:
well formed below the isoelectric p
Page 59 and 60:
2.1.2. Nonsurfactant Templates and
Page 61 and 62:
since controllable partial removal
Page 63 and 64:
were ground manually into fine powd
Page 65 and 66:
volatile sol-gel reaction byproduct
Page 67 and 68:
After the thermal treatment at 150
Page 69 and 70:
oiling point of benzoin (i.e., 194
Page 71 and 72:
interconnected pores or channels wi
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6. Huo, Q.; Magargolese, D. I.; Cie
Page 75 and 76:
Table 2-1. Composition and pore par
Page 77 and 78:
Weight (%) 100 80 60 40 20 0 0 100
Page 79 and 80:
Weight (%) 100 90 80 70 60 0 100 20
Page 81 and 82:
Weight (%) 100 90 80 70 60 50 40 0
Page 83 and 84:
Figure 2-7. Representative IR spect
Page 85 and 86:
dV/dD Pore Volume (cm 3 g -1 Å -1
Page 87 and 88:
dv/dD, Pore Volume (cm 3 g -1 Å -1
Page 89 and 90:
Net Pore Volume (cm 3 g -1 ) 0.6 0.
Page 91 and 92:
Chapter 3. Synthesis of Mesoporous
Page 93 and 94:
preparation conditions. In general,
Page 95 and 96:
cubic, as well as vesicular structu
Page 97 and 98:
3.2 Experimental The synthesis appr
Page 99 and 100:
3.2.3. Synthesis of Mesoporous Sphe
Page 101 and 102:
fructose is incorporated into the s
Page 103 and 104:
mainly attributed to the monolayer-
Page 105 and 106:
with nonsurfactant templates at dif
Page 107 and 108:
3.4. Conclusions and Remarks In the
Page 109 and 110:
11. Matijević, E.; Gheradi, P. Tra
Page 111 and 112:
41. Polarz, S.; Smarsly, B.; Bronst
Page 113 and 114:
(a) (b) Figure 3-1. Typical SEM ima
Page 115 and 116:
Volume Adsorbed (cm 3 g -1 , STP) 3
Page 117 and 118:
Figure 3-5. Representative TEM imag
Page 119 and 120:
(a) (b) Figure 3-7. Typical SEM ima
Page 121 and 122:
Chapter 4. Synthesis of Mesoporous
Page 123 and 124:
nm, and the reaction reaches the hi
Page 125 and 126:
microemulsion. 39 Martino et al. re
Page 127 and 128:
the colloidal gold sol was combined
Page 129 and 130:
holders with adhesive carbon tape.
Page 131 and 132:
trapped in the gold-silica matrix,
Page 133 and 134:
108 The Barrett-Joyner-Halenda (BJH
Page 135 and 136:
indicative of a well-defined crysta
Page 137 and 138:
(i.e., 2-50 nm). Combining both hig
Page 139 and 140:
19. Hayashi, T.; Tanaka, K.; Haruta
Page 141 and 142:
53. Qi, L.; Ma, J.; Cheng, H.; Zhao
Page 143 and 144:
Figure 4-1. Representative X-ray en
Page 145 and 146:
Pore Volume (cm 3 g -1 A -1 ) 0.06
Page 147 and 148:
(a) (b) 122 Figure 4-5. (a) Represe
Page 149 and 150:
Absorbance Wavelength (nm) Figure 4
Page 151 and 152:
5.1.1. Organic-Inorganic Nanocompos
Page 153 and 154:
128 We are also interested in the p
Page 155 and 156:
mica and graphite, the top layer wa
Page 157 and 158:
mode. Scanning electron microscopy
Page 159 and 160:
Waal’s forces), the agglomeration
Page 161 and 162:
136 A single glass transition tempe
Page 163 and 164:
5.5. Acknowledgments 138 I want to
Page 165 and 166:
30. Dimitrov, A. S.; Nagayama, K. L
Page 167 and 168:
(a) (b) 142 Figure 5-2. Representat
Page 169 and 170:
144 Figure 5-4. Representative AFM
Page 171 and 172:
Figure 5-6. Representative IR spect
Page 173 and 174:
(a) (b) Figure 5-8. Representative
Page 175 and 176:
the possibility of utilizing conduc
Page 177 and 178:
iocompatibility and water solubilit
Page 179 and 180:
emeraldine salt, the unique conduct
Page 181 and 182:
acid (HCl, 37.3%, Fisher), hydrogen
Page 183 and 184:
the surface of polymer coated cultu
Page 185 and 186:
acidic acid aqueous solution showed
Page 187 and 188:
oxidant, indicating the formation o
Page 189 and 190:
complex was synthesized by pre-alig
Page 191 and 192:
8. Epstein, A. J. Springer Ser. Mat
Page 193 and 194:
45. Liu, J.-M.; Yang, S. Chem. Comm
Page 195 and 196:
Figure 6-1. Schematics of biologica
Page 197 and 198:
172 Figure 6-3. UV-Vis absorption s
Page 199 and 200:
Figure 6-5. FT-IR spectra of (a) co
Page 201 and 202:
176 Figure 6-7. UV-Vis absorption s
Page 203 and 204:
(a) (b) 178 Figure 6-9. Comparison
Page 205 and 206:
prepared and purified as substitute
Page 207 and 208:
greatest advantages of organic mate
Page 209 and 210:
een explored as a direct and effect
Page 211 and 212:
if we could fine-tune the carrier t
Page 213 and 214:
NMR (250 MHz, DCCl3) δ (ppm): 8.95
Page 215 and 216:
7.2.4. Instrumentation and Characte
Page 217 and 218:
The absence of the proton from the
Page 219 and 220:
194 The absorbance at 600 nm is the
Page 221 and 222:
L3Al dissociated to free ligand (L)
Page 223 and 224:
198 State and Integrated Circuit Te
Page 225 and 226:
34. Stossel, M.; Staudigel, J.; Ste
Page 227 and 228:
Table 7-1. The UV absorbance at 600
Page 229 and 230:
Figure 7-2. Schematic cross-section
Page 231 and 232:
Figure 7-4. NMR Spectra of ligand 1
Page 233 and 234:
Figure 7-6. FT-IR spectra of (a) li
Page 235 and 236:
Figure 7-8. During air oxidation: 1
Page 237 and 238:
[A] 1.2E-04 1.0E-04 8.0E-05 6.0E-05
Page 239 and 240:
Figure 7-12. Mass spectrum of alumi
Page 241 and 242:
Chapter 8. Concluding Remarks 216 T
Page 243 and 244:
218 In contrast to the conventional
Page 245 and 246:
properties of gold nanoparticles ma
Page 247 and 248:
222 In an effort to obtain new elec
Page 249 and 250:
as sensor units, the biodegradable
Page 251 and 252:
polyanhydrides, 4 polyorthoesters,
Page 253 and 254:
substitution reaction, several hund
Page 255 and 256:
polyphosphazenes. Obtained material
Page 257 and 258:
polyphosphazene network. Studies in
Page 259 and 260:
matrix is readily formed due to the
Page 261 and 262:
236 The delivery system can be made
Page 263 and 264:
phosphazene main chains. Further in
Page 265 and 266:
9. Allcock, H. R. Adv. Mater. 1994,
Page 267 and 268:
Figure A-1. Repeating unit in polyp
Page 269 and 270:
Figure A-3. Applications of materia
Page 271 and 272:
Figure A-5. Preparation of poly(N-i
Page 273 and 274:
B.3. Acknowledgments 248 I am grate
Page 275 and 276:
Figure B-2. Cyclic voltammogram (Hg
Page 277 and 278:
Figure B-4. Cyclic voltammogram (Pt
Page 279 and 280:
Figure B-6. Cyclic voltammogram (Hg
Page 281 and 282:
Figure B-8. Cyclic voltammogram (Pt
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