Handbook of Size Exclusion Chromatography and Related ...

More documents

Recommendations

Info

155. PW Jennings, JAS Pribanic, TM Mendes, JA Smith. In: J Youtcheff, T Mill, co-chairmen. Symposia of Chemistry and Characterization of Asphalts. Washington, D.C.: American Chemical Society, 35(3):383–388, 1990. 156. HV Drushel. In: PC Uden, S Siggia, eds. Analytical Chemistry of Liquid Fuel Sources. Advances in Chemistry Series 170. Washington, D.C.: American Chemical Society, 1978, pp 295–306. 157. EW Albaugh, PC Talarico. J Chromatogr 74:233–253, 1972. 158. JB Dixon. Chimia 38(3):82–86, 1984. 159. CD Pearson, SG Gharfeh. Anal Chem 58:307–311, 1986. 160. S Coulombe. J Chromatogr Sci 26:1–6, 1988. 161. TH Mourey, LE Oppenheimer. Anal Chem 56:2427–2434, 1984. 162. M Righezza, G Guiochon. J Liq Chromatogr 11(9/10):1967–2004, 1988. 163. KD Bartle, M Burke, DG Mills, S Pape, S Lu. In: J Youtcheff, T Mill, co-chairmen. Symposia of Chemistry and Characterization of Asphalts. Washington, D.C.: American Chemical Society, 35(3):415–420, 1990. 164. KD Bartle, M Burke, DG Mills, S Pape, S-L Lu. Fuel Sci Technol Int 10(4–6):1071–1082, 1992. 165. M Haney. American Laboratory, March and April, 1985. 166. M Haney. U.S. Patent No. 4,463,598. Official Gazette 54, August 7, 1984. 167. CD Pearson, JB Green. Fuel 68:465–474, 1989. © 2004 by Marcel Dekker, Inc.
9 Size Exclusion Chromatography of Acrylamide Homopolymer and Copolymers Fu-mei C. Lin University of Pittsburgh Pittsburgh, Pennsylvania, U.S.A. 1 INTRODUCTION Acrylamide monomer is a white crystal, available commercially as a 50 wt% aqueous solution. Acrylamide monomer can be polymerized to a very-highmolecular-weight (10 6 –10 7 g/mole) homopolymer, copolymer, or terpolymer. Polyacrylamide (PAM) is a nonionic polymer. The anionic polyacrylamide species can be obtained from the hydrolysis of the amide ( 2CONH 2) functional group of the homopolymer, or from the copolymerization of acrylamide with an anionic monomer, such as acrylic acid (AA) or 2-acrylamino 2-methyl propane sulfonic acid (AMPS). Acrylamide can be copolymerized with a cationic monomer, such as dimethyl diallylammonium chloride (DMDAAC) or acryloyloxyethyl trimethyl ammonium chloride (ALETAC), to form the cationic acrylamide polymer. © 2004 by Marcel Dekker, Inc.
Page 1 and 2:
MARCEL DEKKER Handbook of Size Excl
Page 3 and 4:
CHROMATOGRAPHIC SCIENCE SERIES A Se
Page 5 and 6:
60. Modern Chromatographic Analysis
Page 7 and 8:
Preface to the Second Edition Gel p
Page 9 and 10:
Preface to the First Edition Molecu
Page 11 and 12:
Contents Preface to the Second Edit
Page 13 and 14:
17. Size Exclusion Chromatography o
Page 15 and 16:
James F. Curry Analytical Departmen
Page 17 and 18:
Iwao Teraoka, Ph.D. Othmer Departme
Page 19 and 20:
The graphical data display typicall
Page 21 and 22:
polymer molecule can elute. The tot
Page 23 and 24:
individual states) allowed to them.
Page 25 and 26:
unsaturation while the IR detector
Page 27 and 28:
Sampleconcentrationshouldbeminimize
Page 29 and 30:
averagesdefinedintermsofthemolecula
Page 31 and 32:
information regarding appropriate M
Page 33 and 34:
Analytical. Two models, the KMX-6 a
Page 35 and 36:
Figure 6 Overlay of time-sliced pea
Page 37 and 38:
accurately for very large and very
Page 39 and 40:
4 GENERAL REFERENCES The interested
Page 41 and 42:
46. TA Chamberlin, HE Tuinstra. US
Page 43 and 44:
materials are commercially availabl
Page 45 and 46:
Table 1 Commercial Column Packing M
Page 47 and 48:
necessarily comparable. For this re
Page 49 and 50:
adjusted such that the pore size di
Page 51 and 52:
narrowmolecular weight range, indiv
Page 53 and 54:
Figure 8 Effect of particle size on
Page 55 and 56:
Figure 9 SEC calibration using poly
Page 57 and 58:
Table 4 Typical Eluent Systems for
Page 59 and 60:
Figure 12 Analysis of poly-2-vinyl
Page 61 and 62:
24. E Meehan, S O’Donohue. The ro
Page 63 and 64:
into accepted laboratory techniques
Page 65 and 66:
Table 1 Trace Metal Impurities in C
Page 67 and 68:
mass and biological activity, for m
Page 69 and 70:
Experimental efficiency vs. velocit
Page 71 and 72:
Table 3 Properties of SEC Silica Ge
Page 73 and 74:
operate at aflow rate that can easi
Page 75 and 76:
Figure 3 Efficiency of amide-bonded
Page 77 and 78:
mechanically stable packing materia
Page 79 and 80:
Figure 5 Pore size distributions of
Page 81 and 82:
Figure 6 Separation of polystyrenes
Page 83 and 84:
60-120 A ˚ are large enough to be
Page 85 and 86:
Table 6 Selected Silica-Based Colum
Page 87 and 88:
Table 7 Separation Ranges for Polym
Page 89 and 90:
the decline in permeability is perm
Page 91 and 92:
sample components can be varied by
Page 93 and 94:
Figure 10 Diol bonding reactions. I
Page 95 and 96:
ecause of the higher relative molec
Page 97 and 98:
valuesfork1,k2,anda,theunknownmolec
Page 99 and 100:
water-soluble and detergent-soluble
Page 101 and 102:
the importance of secondary retenti
Page 103 and 104:
discussed in Table 8(33). Based on
Page 105 and 106:
individual dispersion processes ins
Page 107 and 108:
The detector time constant can dist
Page 109 and 110:
5.3 Mobile Phase A mobile phase is
Page 111 and 112:
less steep and still linear at high
Page 113 and 114:
35. P Bristow, J Knox. Chromatograp
Page 115 and 116:
112. K Gooding, K Lu, G Vanecek, F
Page 117 and 118:
for branched polymers or copolymers
Page 119 and 120:
Figure 1 “Bridge design” flow-r
Page 121 and 122:
Figure 3 A light-scattering photome
Page 123 and 124:
Figure 5 SEC universal calibration
Page 125 and 126:
where hn is the hydrodynamic volume
Page 127 and 128:
It should be noted that dn=dc also
Page 129 and 130:
sensitivity for many samples compar
Page 131 and 132:
that is, log[h] vs. logM,generated
Page 133 and 134:
Figure 8 Effect of band broadening
Page 135 and 136:
Table 1 Measurement of Molecular We
Page 137 and 138:
Figure 10 Differential refractomete
Page 139 and 140:
Figure 11 (A) Mark-Houwink plot of
Page 141 and 142:
Table 3 Measurement of Molecular We
Page 143 and 144:
size information is derived from un
Page 145 and 146:
Table 5 Molecular Weight Distributi
Page 147 and 148:
By measuring the scattered intensit
Page 149 and 150:
8 APPENDIX: INSTRUMENT COMPANIES 8.
Page 151 and 152:
53. G Marot, J Lesec. J Liq Chromat
Page 153 and 154:
125. D Slootmaekers, JAPP Van Dijk,
Page 155 and 156:
200. JG Bindels, GJJ Bessems, BM De
Page 157 and 158:
possibly with hydrodynamic volume (
Page 159 and 160:
An insurmountable limitation of SEC
Page 161 and 162:
to sDR(V) when either nPS ¼nPB ¼c
Page 163 and 164:
1,4-trans;and8%1,2-vynil.TheglobalC
Page 165 and 166:
The goal is to find the MWD and CCD
Page 167 and 168:
As expected, pS is closer to the no
Page 169 and 170:
Figure 3 Example 3: MWD and BD of a
Page 171 and 172:
9. BH Zimm, WH Stockmayer. The dime
Page 173 and 174:
45. RO Bielsa, GR Meira. Linear cop
Page 175 and 176:
solubility properties. They are use
Page 177 and 178:
determination of the absolute molec
Page 179 and 180:
Figure 4 Result of the PBT analysis
Page 181 and 182:
Figure 8 Result of natural spider s
Page 183 and 184:
7 Size Exclusion Chromatography of
Page 185 and 186:
As pointed out earlier, rubber must
Page 187 and 188:
Table 2 Various Solvents and Operat
Page 189 and 190:
Figure 2 Typical GPC calibrations w
Page 191 and 192:
© 2004 by Marcel Dekker, Inc. Figu
Page 193 and 194:
Natural and Synthetic Rubbe177 vari
Page 195 and 196:
Another example, shown in Fig. 5 (3
Page 197 and 198:
APPENDIX: SEC CONDITIONS FOR RUBBER
Page 199 and 200:
Appendix (Continued) Polymer Column
Page 201 and 202: Appendix (Continued) Polymer Column
Page 205 and 206: 5. J West, E Rodriguez. Rubber Chem
Page 207 and 208: 8 Size Exclusion Chromatography of
Page 209 and 210: associate. Girdler (67) and Speight
Page 211 and 212: Table 1 Fractions Obtained Using Co
Page 213 and 214: Figure 1 SEC analyses of an aged as
Page 215 and 216: Apparently more polar compounds are
Page 217 and 218: 40% was fractionated into four frac
Page 219 and 220: Figure 7 SEC analyses of an unaged
Page 221 and 222: Figure 9 Comparison of percentage L
Page 223 and 224: Figure 11 Comparison of SEC chromat
Page 225 and 226: Figure 12 Comparisons of SEC chroma
Page 227 and 228: percentage LMS at the other locatio
Page 229 and 230: the total area into up to 12 sectio
Page 231 and 232: attempted to develop an SEC method
Page 233 and 234: parameterisbasedontheinternalpressu
Page 235 and 236: 5 MODIFIED ASPHALTS The addition of
Page 237 and 238: Oxidation of the rubber and asphalt
Page 239 and 240: Figure 20 SEC chromatogram for an a
Page 241 and 242: Figure 21 Comparisons of apparent m
Page 243 and 244: © 2004 by Marcel Dekker, Inc. S/
Page 245 and 246: PS/10 4 þ 10 3 þ 500 þ 100 THF/1
Page 247 and 248: Nevertheless, SEC of asphalts is es
Page 249 and 250: 56. NW Garrick, RR Biskur. Trans Re
Page 251: Asphalts 235 122. M-S Lin, JM Chaff
Page 255 and 256: Table 1 Applications of Acrylamide
Page 257 and 258: (AM/AA), and acrylamide/dimethyldia
Page 259 and 260: polymer, a large size filter of 5,
Page 261 and 262: Figure 1 Size exclusion chromatogra
Page 263 and 264: Table3 MWandMWDofaBroad-MWDPAMStand
Page 265 and 266: Another commercially available MW d
Page 267 and 268: Table 5 Weight-Average Molecular We
Page 269 and 270: Figure 6 (a) Size exclusion chromat
Page 271 and 272: compared to anormal product. By com
Page 273 and 274: StudyingtheKineticsofaChemicalReact
Page 275 and 276: this information, the higher MW pea
Page 281 and 282: 46. CJ Kim, A Hamielec, A Bendek. J
Page 283 and 284: 10 Size Exclusion Chromatography of
Page 285 and 286: A relatively new technique utilizin
Page 287 and 288: where ais the exponent of the Mark-
Page 289 and 290: Figure 2 TDS chromatograms for full
Page 291 and 292: Figure 5 Comparison of molecular we
Page 293 and 294: Table 3 Summary of TDS Molecular We
Page 295 and 296: thepartiallyhydrolyzedPVAwiththecol
Page 297 and 298: Table 5 Summary of Conformation and
Page 299 and 300: a¼0.627andlog(K) ¼23.249.Theseare
Page 301 and 302: The limits of detection of the PVA
Page 303 and 304:
Figure 12 PVAc broad molecular weig
Page 305 and 306:
4 SUMMARY Advances in SEC character
Page 307 and 308:
Page 309 and 310:
2.1 Molecular Weight Grades of PVP
Page 311 and 312:
exclusion chromatography with low-a
Page 313 and 314:
weightandmolecularweightdistributio
Page 315 and 316:
Page 317 and 318:
Figure 4 PEOcalibrationofUltrahydro
Page 319 and 320:
Figure 6 Overlay of GPC chromatogra
Page 321 and 322:
plus Ultrahydrogel 120 A ˚ ,Shodex
Page 323 and 324:
Figure 10 SEC traces of PVP/AA copo
Page 325 and 326:
Figure 11 Molecular weight distribu
Page 327 and 328:
Page 329 and 330:
2 CHEMICAL, MACROMOLECULAR AND MORP
Page 331 and 332:
Table 2 The Relative Composition of
Page 333 and 334:
considered to be 3. After the DS ha
Page 335 and 336:
een extensively studied by methods
Page 337 and 338:
The silylation was performed in LiC
Page 339 and 340:
observed using column materials hav
Page 341 and 342:
Table 6 (Continued) Packing materia
Page 343 and 344:
4.5 Other Cellulose Derivatives Bes
Page 345 and 346:
Table 8 SEC Conditions for Characte
Page 347 and 348:
dextrans swell too much in cadoxen
Page 349 and 350:
stirring at room temperature for an
Page 351 and 352:
Figure 2 MMDofunbleached(HP)andblea
Page 353 and 354:
Figure 4 MMDofbirchkraftpulpdegrade
Page 355 and 356:
adequate when evaluating the influe
Page 357 and 358:
differential refractive index (DRI)
Page 359 and 360:
30. HA Krässig. Effects of structu
Page 361 and 362:
67. E Sjöholm, K Gustafsson, A Col
Page 363 and 364:
104. B Fleury, J Dubois, C Léonard
Page 365 and 366:
136. D Miller, D Senior, R Sutcliff
Page 367 and 368:
166. SS Cutié, CG Smith. Determina
Page 369 and 370:
200. R Berggren, F Berthold, E Sjö
Page 371 and 372:
13 Molar Mass and Size Distribution
Page 373 and 374:
measurements, and vapor pressure os
Page 375 and 376:
The calibration of SEC columns by c
Page 377 and 378:
The division according to eluent ty
Page 379 and 380:
Apolymer produced by UV irradiation
Page 381 and 382:
Because DMAC/LiCl is also agood sol
Page 383 and 384:
compoundsandwasexplainedbyadsorptio
Page 385 and 386:
isolated lignins because they are e
Page 387 and 388:
The Separon HEMA and Separon HEMA B
Page 389 and 390:
Figure 4 GPC elution curves of the
Page 391 and 392:
liquor is highest throughout the co
Page 393 and 394:
topological anisotropy in the polym
Page 395 and 396:
29. M Ristolainen, R Alen, J Knuuti
Page 397 and 398:
eds. Proc Int Symp 1998. Canton, Pe
Page 399 and 400:
92. L Jurasek. Towards a three dime
Page 401 and 402:
Table 1 Selected Industries Connect
Page 403 and 404:
into C3-metabolites, which then may
Page 405 and 406:
Table 4 Key Enzymes in the Biosynth
Page 407 and 408:
Table 5 Cloned Mutants of Starch En
Page 409 and 410:
Figure 3 Modeled x-ray diffraction
Page 411 and 412:
In the native environment (plant ce
Page 413 and 414:
Figure 6 (a) Large starch granules
Page 415 and 416:
number of branching points); crossl
Page 417 and 418:
Both absolute approaches are extrao
Page 419 and 420:
Table 7 (Continued) Approach Experi
Page 421 and 422:
structures, excluded volumes, and t
Page 423 and 424:
Figure 10 (a) SEC elution profile o
Page 425 and 426:
Figure 12 Wheat glucans: DRI elutio
Page 427 and 428:
Figure 13 Wheat glucans. Normalized
Page 429 and 430:
Figure 16 Wheat glucan. Normalized
Page 431 and 432:
Figure 18 Wheat glucan.Elution prof
Page 433 and 434:
Figure 20 Wheat glucans. Absolute m
Page 435 and 436:
Figure 22 Wheat glucan. (a) Intrins
Page 437 and 438:
Figure 24 Wheat PA-glucan. Elution
Page 439 and 440:
an Ubbelohde-viscometer for concent
Page 441 and 442:
Rheological investigations of stabi
Page 443 and 444:
shifts to applied laser light, whic
Page 445 and 446:
Table 8 Characteristic Parameters f
Page 447 and 448:
Table 8 (Continued) and H2O. A part
Page 449 and 450:
10. SG Ball, MHBJ van de Wal, RGF V
Page 451 and 452:
52. W Praznik, R Beck. J Chromatogr
Page 453 and 454:
Page 455 and 456:
3 PROTEIN PARTITIONING IN SEC 3.1 G
Page 457 and 458:
Figure 1 Plot of Kav vs. log M for
Page 459 and 460:
yconsideringtheproteinsolutestobesp
Page 461 and 462:
globular proteins and selected flex
Page 463 and 464:
silanol groups (52-54); even capped
Page 465 and 466:
most proteins to be maximally stabl
Page 467 and 468:
Figure 4 Chromatograms of BSA and P
Page 469 and 470:
concentrated) steps of protein puri
Page 471 and 472:
Table 3 Characteristics of Dextran-
Page 473 and 474:
preparative SEC. The capabilities o
Page 475 and 476:
37. GR Noll, N Nagle, JO Baker, DJ
Page 477 and 478:
Page 479 and 480:
Figure 2 Separation of total E. col
Page 481 and 482:
Figure 3 Separation of HaeIII-cleav
Page 483 and 484:
The recovery of DNA fragments has b
Page 485 and 486:
Endotoxin should also be removed fr
Page 487 and 488:
Table 3 Best Columns for the Separa
Page 489 and 490:
Figure 10 Dependence of HETP on flo
Page 491 and 492:
Appendix (Continued ) Polymer Colum
Page 493 and 494:
REFERENCES 1. CT Wehr, SR Abbott. J
Page 495 and 496:
MALDI-MS has been applied to determ
Page 497 and 498:
Figure 1 Calibration curvesof SEC c
Page 499 and 500:
Figure 3 Chromatograms of epoxy res
Page 501 and 502:
wherenandn0 aretheRIsofthesample an
Page 503 and 504:
Figure 5 SEC chromatogram of n-alka
Page 505 and 506:
Figure 7 Refractive indexes of comm
Page 507 and 508:
Another detector recently applied i
Page 509 and 510:
Figure 11 Absolute MW calibration p
Page 511 and 512:
Figure 12 Chromatogram of Acrawax C
Page 513 and 514:
18 Two-Dimensional Liquid Chromatog
Page 515 and 516:
largerispressuredropandresultingexp
Page 517 and 518:
elations between molar masses and s
Page 519 and 520:
Figure 2 (Continued) chapter, one o
Page 521 and 522:
where Nis the column efficiency exp
Page 523 and 524:
composition/architecture/molar mass
Page 525 and 526:
solvent. Here again, solvent-solven
Page 527 and 528:
or repulsive interactions between m
Page 529 and 530:
macromolecules may strongly differ
Page 531 and 532:
temperature. The efficacy of an ads
Page 533 and 534:
however, aliphatic bonded groups ma
Page 535 and 536:
Figure 10 Schematic representation
Page 537 and 538:
packing materials for SEC of synthe
Page 539 and 540:
Quantitative relations between sila
Page 541 and 542:
Both strength and thermodynamic qua
Page 543 and 544:
where Cand Dare constants for apart
Page 545 and 546:
ThisisimportantwhenLCCCisappliedtoc
Page 547 and 548:
Page 549 and 550:
Page 551 and 552:
However, strong adsorption of macro
Page 553 and 554:
elution step may be sufficient for
Page 555 and 556:
Figure 16 Block scheme of a full ad
Page 557 and 558:
processing of 2D-HPLC data. Knowled
Page 559 and 560:
Figure 20 Set of full retention-elu
Page 561 and 562:
distributions of complex polymers a
Page 563 and 564:
constituents were not discriminated
Page 565 and 566:
(Sec. 7) and therefore they can be
Page 567 and 568:
2. Identify sample solvents. First
Page 569 and 570:
1 Segmental interaction energy para
Page 571 and 572:
58. BG Belenkii. Pure Appl Chem 51:
Page 573 and 574:
19 Methods and Columns for High-Spe
Page 575 and 576:
Table 1 Summary of Methods for Incr
Page 577 and 578:
not savealot of time and solvent, d
Page 579 and 580:
Figure 3 Conventional SEC chromatog
Page 581 and 582:
chromatogram at 4mL/min, which is f
Page 583 and 584:
Sincethereductionoftheinternaldiame
Page 585 and 586:
Table 3 Summary of Column Performan
Page 587 and 588:
Figure 11 Dependence of column perf
Page 589 and 590:
. Two-dimensional chromatography ru
Page 591 and 592:
The standard deviations for the mol
Page 593 and 594:
Figure 15 Comparison of time requir
Page 595 and 596:
Figure 17 Accuracy and precision of
Page 597 and 598:
polymer analysis. Samples are “ru
Page 599 and 600:
just ignoring the fractionation of
Page 601 and 602:
20 Automatic Continuous Mixing Tech
Page 603 and 604:
out at low enough concentration tha
Page 605 and 606:
educed viscosity, h r, to be comput
Page 607 and 608:
Page 609 and 610:
Figure 2 Raw ACOMP signals from mul
Page 611 and 612:
Figure 4 Mw vs. monomer conversion,
Page 613 and 614:
decreases smoothly and monotonicall
Page 615 and 616:
Figure 7 Effects of fluctuating rea
Page 617 and 618:
Finally, the use of a light-scatter
Page 619 and 620:
Figure 8 Linear and cubic increases
Page 621 and 622:
where r(t) is now given by 2 6 r(t)
Page 623 and 624:
Figure 11 Light scattering from sol
Page 625 and 626:
3.1 ASimple System: Equilibrium Cha
Page 627 and 628:
Figure 13 (a) ACM applied to the ch
Page 629 and 630:
Also of note in Fig. 13b is how hig
Page 631 and 632:
15. JM Starita, CL Rohn. Rheologica
Page 633 and 634:
52. M Hulden. Hydrophobically modif
Page 635 and 636:
21 Light Scattering and the Solutio
Page 637 and 638:
therefore, is to remove any lingeri
Page 639 and 640:
is often found in the literature wh
Page 641 and 642:
Figure 2 Configuration of an SEC se
Page 643 and 644:
5 THE IMPORTANCE OF SOFTWARE Like a
Page 645 and 646:
standard deviations of the measured
Page 647 and 648:
These include the differential weig
Page 649 and 650:
Figure 8 Data of Fig. 7corrected fo
Page 651 and 652:
Figure 11 Data of Fig. 10 with spik
Page 653 and 654:
Figure 13 Fitstodatacollectedatasli
Page 655 and 656:
Table 1 Errors (in %) Characteristi
Page 657 and 658:
homogeneous copolymer, that is, tak
Page 659 and 660:
process may be used to identify the
Page 661 and 662:
fractionated sample. They represent
Page 663 and 664:
Figure 16 An example of poor SEC ch
Page 665 and 666:
on) methods, whereby the average di
Page 667 and 668:
23. WH Stockmayer, LD Moore Jr, M F
Page 669 and 670:
condition, as is explained in this
Page 671 and 672:
Figure 2 Partition coefficients KL
Page 673 and 674:
4 COLUMNS FOR HOPC Detailsaregiveni
Page 675 and 676:
and concomitant clogging of columns
Page 677 and 678:
Figure 5 Concentration dependence o
Page 679 and 680:
Table 1 Solution Volume, Polymer Ma
Page 681 and 682:
in Fig. 4a. The middle fractions (8
Page 683 and 684:
Figure 10 SEC chromatograms for som
Page 685 and 686:
appropriate for the early fractions
Page 687 and 688:
23 Size Exclusion/ Hydrodynamic Chr
Page 689 and 690:
Figure 2 Calibration curve for the
Page 691 and 692:
Figure 5 Elutionbehaviorofpolystyre
Page 693 and 694:
Table 1 Comparison Between SEC and
Page 695 and 696:
egular SEC column in which the pore
Page 697:
Such an ideal separation can be obt
show all

Handbook of Size Exclusion Chromatography and Related ...

Create successful ePaper yourself

Delete template?

Save as template?