Supramolecular Assembly and Reversible Transition and of Chitosan Fluorescent Micelles by Noncovalent Modulation

<div>(a) TEM image of the micelles at <span class="nowrap"><svg height="11.6934pt" id="M22" style="vertical-align:-3.168421pt" version="1.1" viewbox="-0.0498162 -8.52498 38.1193 11.6934" width="38.1193pt" xmlns="http://www.w3.org/2000/svg" xmlns:xlink="http://www.w3.org/1999/xlink"><g transform="matrix(.013,0,0,-0.013,0,0)"><path d="M169 380V459C122 440 66 423 24 416V392C86 384 90 382 90 317V-135C90 -201 81 -207 17 -213V-240H253V-213C176 -207 169 -201 169 -125V6C182 -1 208 -11 238 -12C368 12 487 109 487 260C487 358 421 449 310 449C298 449 279 444 261 433L169 380ZM169 346C196 367 237 389 269 389C341 389 403 329 403 221C403 109 347 37 263 37C228 37 191 53 169 76V346Z"></path></g><g transform="matrix(.013,0,0,-0.013,6.812,0)"><path d="M729 650H468V622C546 615 554 610 554 527V365H213V527C213 610 221 616 297 622V650H38V622C120 616 128 611 128 527V123C128 39 120 34 40 28V0H303V28C221 34 213 40 213 123V322H554V123C554 39 546 34 460 28V0H728V28C647 34 639 39 639 123V527C639 610 647 615 729 622V650Z"></path></g><g transform="matrix(.013,0,0,-0.013,20.465,0)"><path d="M535 323V373H52V323H535ZM535 138V188H52V138H535Z"></path></g><g transform="matrix(.013,0,0,-0.013,31.728,0)"><path d="M412 140C382 77 369 73 315 73H129L270 222C362 320 402 379 402 466C402 571 322 635 234 635C177 635 130 609 99 576L42 495L64 475C90 514 133 568 201 568C274 568 318 519 318 435C318 349 255 267 193 193C144 135 87 78 32 23V0H405C417 45 427 89 440 131L412 140Z"></path></g></svg>.</span> Inset: size distributions of aqueous solutions of chitosan and TPE-(N-COOH)<sub>4</sub> mixture at <span class="nowrap"><svg height="11.6934pt" id="M23" style="vertical-align:-3.168421pt" version="1.1" viewbox="-0.0498162 -8.52498 38.1193 11.6934" width="38.1193pt" xmlns="http://www.w3.org/2000/svg" xmlns:xlink="http://www.w3.org/1999/xlink"><g transform="matrix(.013,0,0,-0.013,0,0)"><path d="M169 380V459C122 440 66 423 24 416V392C86 384 90 382 90 317V-135C90 -201 81 -207 17 -213V-240H253V-213C176 -207 169 -201 169 -125V6C182 -1 208 -11 238 -12C368 12 487 109 487 260C487 358 421 449 310 449C298 449 279 444 261 433L169 380ZM169 346C196 367 237 389 269 389C341 389 403 329 403 221C403 109 347 37 263 37C228 37 191 53 169 76V346Z"></path></g><g transform="matrix(.013,0,0,-0.013,6.812,0)"><path d="M729 650H468V622C546 615 554 610 554 527V365H213V527C213 610 221 616 297 622V650H38V622C120 616 128 611 128 527V123C128 39 120 34 40 28V0H303V28C221 34 213 40 213 123V322H554V123C554 39 546 34 460 28V0H728V28C647 34 639 39 639 123V527C639 610 647 615 729 622V650Z"></path></g><g transform="matrix(.013,0,0,-0.013,20.465,0)"><path d="M535 323V373H52V323H535ZM535 138V188H52V138H535Z"></path></g><g transform="matrix(.013,0,0,-0.013,31.728,0)"><path d="M412 140C382 77 369 73 315 73H129L270 222C362 320 402 379 402 466C402 571 322 635 234 635C177 635 130 609 99 576L42 495L64 475C90 514 133 568 201 568C274 568 318 519 318 435C318 349 255 267 193 193C144 135 87 78 32 23V0H405C417 45 427 89 440 131L412 140Z"></path></g></svg>.</span> (b) The zeta potential of micelles at different pH values. pH-dependence fluorescence emission spectra recorded for the aqueous solution of (c) WCS/TPE-(N-COOH)<sub>4</sub> micelles and (d) TPE-(N-COOH)<sub>4</sub> with pH decreasing from 8 to 2, <svg height="12.5612pt" id="M24" style="vertical-align:-3.27287pt" version="1.1" viewbox="-0.0498162 -9.28833 50.2947 12.5612" width="50.2947pt" xmlns="http://www.w3.org/2000/svg" xmlns:xlink="http://www.w3.org/1999/xlink"><g transform="matrix(.013,0,0,-0.013,0,0)"><path d="M529 97L508 118C475 75 449 58 438 58C428 58 421 66 415 104C393 234 374 403 364 496C345 670 307 712 254 712C220 712 174 691 153 669L161 645C176 653 194 658 206 658C237 658 261 640 278 562C287 522 290 483 293 434C223 269 110 105 23 9L32 -12C59 -6 85 0 108 7C152 64 251 252 300 366C307 297 315 221 337 82C346 24 363 -12 393 -12C425 -12 475 13 529 97Z"></path></g><g transform="matrix(.0091,0,0,-0.0091,7.761,3.132)"><path d="M380 106C343 72 306 56 265 56C195 56 116 112 115 248C235 252 361 262 377 265C396 269 400 277 400 297C400 374 333 449 250 449H249C198 449 144 421 103 376S37 269 37 201C37 88 109 -12 232 -12C263 -12 332 6 395 84L380 106ZM225 412C281 412 315 364 314 312C314 297 308 292 290 292C232 290 176 289 120 289C135 370 180 412 225 412Z"></path></g><g transform="matrix(.0091,0,0,-0.0091,11.628,3.132)"><path d="M474 0V26C414 34 401 43 364 100L267 248C300 297 324 332 345 358C381 400 394 405 455 411V437H272V411C316 406 323 401 305 370C287 337 267 306 247 276L188 369C169 397 173 405 215 411V437H16V411C71 404 83 396 114 348L201 212C171 167 144 127 116 92C77 42 66 34 4 26V0H190V26C139 34 136 43 156 77C175 113 198 150 220 183L294 66C311 39 302 31 260 26V0H474Z"></path></g><g transform="matrix(.013,0,0,-0.013,20.084,0)"><path d="M535 323V373H52V323H535ZM535 138V188H52V138H535Z"></path></g><g transform="matrix(.013,0,0,-0.013,31.347,0)"><path d="M285 378C315 398 338 416 353 432C373 451 384 474 384 503C384 579 325 635 236 635H235C182 635 136 610 108 579L65 516L85 496C110 533 150 575 205 575C258 575 300 543 300 481C300 407 232 369 141 339L147 310C163 315 188 321 211 321C268 321 338 284 338 192C338 94 288 40 217 40C160 40 119 68 93 91C85 98 77 97 69 91C60 84 47 71 46 58C44 46 48 35 62 22C75 10 116 -12 162 -12C234 -12 424 62 424 224C424 297 373 359 285 376V378Z"></path></g><g transform="matrix(.013,0,0,-0.013,37.587,0)"><path d="M456 178V225H360V632H320C217 496 115 347 20 206V178H280V106C280 40 276 34 189 27V0H445V27C364 34 360 39 360 106V178H456ZM280 225H82C149 335 214 431 278 520H280V225Z"></path></g><g transform="matrix(.013,0,0,-0.013,43.828,0)"><path d="M153 550H386L412 615L406 623H120L82 318C104 327 142 338 184 338C294 338 347 275 347 187C347 112 305 39 221 39C160 39 119 71 97 89C88 97 80 96 71 90C59 80 50 67 49 57C48 45 52 36 66 23C80 9 123 -12 169 -12C221 -11 288 15 342 59C403 109 431 165 431 225C431 308 366 395 238 395C212 395 165 379 127 364L153 550Z"></path></g></svg> nm, 25°C. The molar ratio of [NH<sub>3</sub><sup>+</sup>]/[COO<sup>-</sup>] was 1.0, and the TPE-(N-COOH)<sub>4</sub> concentration was fixed at 1.0 g/L in all cases.</div>

Advances in Polymer Technology

fig5

Figure 5

Figure 5: Supramolecular Assembly and Reversible Transition and of Chitosan Fluorescent Micelles by Noncovalent Modulation 