Handbook of Size Exclusion Chromatography and Related ...

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amorphous lcb-glucans by encapsulation. From such granules lcbglucans (amylose) may even be extracted by leaching processes that similarly reduce the amorphous layer fraction. . Amylomaize starch granules are composed of a minor fraction of 30% of scb-glucans (amylopectin) and a major fraction of 70% of lcb-glucans (amylose) with pronounced separation of scb- and lcbglucans. On hydration lcb-glucans of such granules are diluted, but the granules do not swell. From such granules lcb-glucans may be extracted by leaching processes. Starch granules (Fig. 4) are composed of a crystalline scb-glucan (amylopectin) framework and an amorphous lcb-glucan (amylose) fraction. Glucans of scb- and lcb-type are more or less incompatible: scb-glucans (amylopectin) form compact layers of high order lcb-glucans (amylose) form amorphous precipitates in less dense domains. Within the granules the tendency for separation increases with increasing percentage of lcb-glucans in a mixture of both types. No instance of an homogeneous scb/lcb-glucan blend in a starch granule is known. Figure 4 Schematic starch granule architecture with respect to different scb/lcb-glucan ratio and consequences on size and shape upon swelling in aqueous environment. © 2004 by Marcel Dekker, Inc.
In the native environment (plant cell), starch granules are hydrated, and thus in a swollen status. In first order, these conditions match with industrially hydrated starch granules: in both cases the granules show up with increased order (birefringence) and reduced hilum opening. In such swollen granules lcb-glucans (amylose) diffuse out of amorphous regions, and, simultaneously, enable transfer ionic compounds into and out of the granules. Chemistry-supported extraction procedures (leaching) and drying result in the formation of compact granules with cracked hilum. 3 ISOLATION/PURIFICATION OF GLUCANS FROM STARCH RAW MATERIALS Systematic analysis of technological qualities of starch materials includes different levels of information: environmental and biological conditions, granule properties, and molecular characteristics (Fig. 5). Isolation of starch granules from native plant materials includes pulverization and milling of starch-containing parts and subsequent separation of granules from sliced cells with water. A sequence of repeated sieving and washing concludes this first step. In industrial isolation processes, due to technological limitations, an additional level of mechanical, thermal, and chemical stress on the granules cannot generally be avoided. However, the granule status after initial purification strongly controls “starch quality” for subsequent processes. Isolation of cereal starch granules for analytical purposes includes elimination of adsorbed proteins (gluten), which may, for example, be achieved Figure 5 Interdependencies of controlling influences for starch glucan properties. © 2004 by Marcel Dekker, Inc.
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MARCEL DEKKER Handbook of Size Excl
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CHROMATOGRAPHIC SCIENCE SERIES A Se
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60. Modern Chromatographic Analysis
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Preface to the Second Edition Gel p
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Preface to the First Edition Molecu
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Contents Preface to the Second Edit
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17. Size Exclusion Chromatography o
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James F. Curry Analytical Departmen
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Iwao Teraoka, Ph.D. Othmer Departme
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The graphical data display typicall
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polymer molecule can elute. The tot
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individual states) allowed to them.
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unsaturation while the IR detector
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Sampleconcentrationshouldbeminimize
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averagesdefinedintermsofthemolecula
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information regarding appropriate M
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Analytical. Two models, the KMX-6 a
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Figure 6 Overlay of time-sliced pea
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accurately for very large and very
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4 GENERAL REFERENCES The interested
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46. TA Chamberlin, HE Tuinstra. US
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materials are commercially availabl
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Table 1 Commercial Column Packing M
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necessarily comparable. For this re
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adjusted such that the pore size di
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narrowmolecular weight range, indiv
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Figure 8 Effect of particle size on
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Figure 9 SEC calibration using poly
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Table 4 Typical Eluent Systems for
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Figure 12 Analysis of poly-2-vinyl
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24. E Meehan, S O’Donohue. The ro
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into accepted laboratory techniques
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Table 1 Trace Metal Impurities in C
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mass and biological activity, for m
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Experimental efficiency vs. velocit
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Table 3 Properties of SEC Silica Ge
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operate at aflow rate that can easi
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Figure 3 Efficiency of amide-bonded
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mechanically stable packing materia
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Figure 5 Pore size distributions of
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Figure 6 Separation of polystyrenes
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60-120 A ˚ are large enough to be
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Table 6 Selected Silica-Based Colum
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Table 7 Separation Ranges for Polym
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the decline in permeability is perm
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sample components can be varied by
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Figure 10 Diol bonding reactions. I
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ecause of the higher relative molec
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valuesfork1,k2,anda,theunknownmolec
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water-soluble and detergent-soluble
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the importance of secondary retenti
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discussed in Table 8(33). Based on
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individual dispersion processes ins
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The detector time constant can dist
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5.3 Mobile Phase A mobile phase is
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less steep and still linear at high
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35. P Bristow, J Knox. Chromatograp
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112. K Gooding, K Lu, G Vanecek, F
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for branched polymers or copolymers
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Figure 1 “Bridge design” flow-r
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Figure 3 A light-scattering photome
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Figure 5 SEC universal calibration
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where hn is the hydrodynamic volume
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It should be noted that dn=dc also
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sensitivity for many samples compar
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that is, log[h] vs. logM,generated
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Figure 8 Effect of band broadening
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Table 1 Measurement of Molecular We
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Figure 10 Differential refractomete
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Figure 11 (A) Mark-Houwink plot of
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Table 3 Measurement of Molecular We
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size information is derived from un
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Table 5 Molecular Weight Distributi
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By measuring the scattered intensit
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8 APPENDIX: INSTRUMENT COMPANIES 8.
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53. G Marot, J Lesec. J Liq Chromat
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125. D Slootmaekers, JAPP Van Dijk,
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200. JG Bindels, GJJ Bessems, BM De
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possibly with hydrodynamic volume (
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An insurmountable limitation of SEC
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to sDR(V) when either nPS ¼nPB ¼c
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1,4-trans;and8%1,2-vynil.TheglobalC
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The goal is to find the MWD and CCD
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As expected, pS is closer to the no
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Figure 3 Example 3: MWD and BD of a
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9. BH Zimm, WH Stockmayer. The dime
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45. RO Bielsa, GR Meira. Linear cop
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solubility properties. They are use
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determination of the absolute molec
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Figure 4 Result of the PBT analysis
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Figure 8 Result of natural spider s
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7 Size Exclusion Chromatography of
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As pointed out earlier, rubber must
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Table 2 Various Solvents and Operat
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Figure 2 Typical GPC calibrations w
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© 2004 by Marcel Dekker, Inc. Figu
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Natural and Synthetic Rubbe177 vari
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Another example, shown in Fig. 5 (3
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APPENDIX: SEC CONDITIONS FOR RUBBER
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Appendix (Continued) Polymer Column
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5. J West, E Rodriguez. Rubber Chem
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associate. Girdler (67) and Speight
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Table 1 Fractions Obtained Using Co
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Figure 1 SEC analyses of an aged as
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Apparently more polar compounds are
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40% was fractionated into four frac
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Figure 7 SEC analyses of an unaged
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Figure 9 Comparison of percentage L
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Figure 11 Comparison of SEC chromat
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Figure 12 Comparisons of SEC chroma
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percentage LMS at the other locatio
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the total area into up to 12 sectio
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attempted to develop an SEC method
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parameterisbasedontheinternalpressu
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5 MODIFIED ASPHALTS The addition of
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Oxidation of the rubber and asphalt
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Figure 20 SEC chromatogram for an a
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Figure 21 Comparisons of apparent m
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© 2004 by Marcel Dekker, Inc. S/
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PS/10 4 þ 10 3 þ 500 þ 100 THF/1
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Nevertheless, SEC of asphalts is es
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56. NW Garrick, RR Biskur. Trans Re
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Asphalts 235 122. M-S Lin, JM Chaff
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Table 1 Applications of Acrylamide
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(AM/AA), and acrylamide/dimethyldia
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polymer, a large size filter of 5,
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Figure 1 Size exclusion chromatogra
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Table3 MWandMWDofaBroad-MWDPAMStand
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Another commercially available MW d
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Table 5 Weight-Average Molecular We
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Figure 6 (a) Size exclusion chromat
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compared to anormal product. By com
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StudyingtheKineticsofaChemicalReact
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this information, the higher MW pea
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46. CJ Kim, A Hamielec, A Bendek. J
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A relatively new technique utilizin
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where ais the exponent of the Mark-
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Figure 2 TDS chromatograms for full
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Figure 5 Comparison of molecular we
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Table 3 Summary of TDS Molecular We
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thepartiallyhydrolyzedPVAwiththecol
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Table 5 Summary of Conformation and
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a¼0.627andlog(K) ¼23.249.Theseare
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The limits of detection of the PVA
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Figure 12 PVAc broad molecular weig
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4 SUMMARY Advances in SEC character
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2.1 Molecular Weight Grades of PVP
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exclusion chromatography with low-a
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weightandmolecularweightdistributio
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Figure 4 PEOcalibrationofUltrahydro
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Figure 6 Overlay of GPC chromatogra
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plus Ultrahydrogel 120 A ˚ ,Shodex
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Figure 10 SEC traces of PVP/AA copo
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Figure 11 Molecular weight distribu
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2 CHEMICAL, MACROMOLECULAR AND MORP
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Table 2 The Relative Composition of
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considered to be 3. After the DS ha
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een extensively studied by methods
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The silylation was performed in LiC
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observed using column materials hav
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Table 6 (Continued) Packing materia
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4.5 Other Cellulose Derivatives Bes
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Table 8 SEC Conditions for Characte
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dextrans swell too much in cadoxen
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stirring at room temperature for an
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Figure 2 MMDofunbleached(HP)andblea
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Figure 4 MMDofbirchkraftpulpdegrade
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adequate when evaluating the influe
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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
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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: Figure 3 Modeled x-ray diffraction
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: 15 Size Exclusion Chromatography of
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
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globular proteins and selected flex
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silanol groups (52-54); even capped
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most proteins to be maximally stabl
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Figure 4 Chromatograms of BSA and P
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concentrated) steps of protein puri
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Table 3 Characteristics of Dextran-
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preparative SEC. The capabilities o
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37. GR Noll, N Nagle, JO Baker, DJ
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Figure 2 Separation of total E. col
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Figure 3 Separation of HaeIII-cleav
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The recovery of DNA fragments has b
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Endotoxin should also be removed fr
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Table 3 Best Columns for the Separa
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Figure 10 Dependence of HETP on flo
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Appendix (Continued ) Polymer Colum
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REFERENCES 1. CT Wehr, SR Abbott. J
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MALDI-MS has been applied to determ
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Figure 1 Calibration curvesof SEC c
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Figure 3 Chromatograms of epoxy res
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wherenandn0 aretheRIsofthesample an
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Figure 5 SEC chromatogram of n-alka
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Figure 7 Refractive indexes of comm
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Another detector recently applied i
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Figure 11 Absolute MW calibration p
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Figure 12 Chromatogram of Acrawax C
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18 Two-Dimensional Liquid Chromatog
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largerispressuredropandresultingexp
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elations between molar masses and s
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Figure 2 (Continued) chapter, one o
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where Nis the column efficiency exp
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composition/architecture/molar mass
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solvent. Here again, solvent-solven
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or repulsive interactions between m
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macromolecules may strongly differ
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temperature. The efficacy of an ads
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however, aliphatic bonded groups ma
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Figure 10 Schematic representation
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packing materials for SEC of synthe
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Quantitative relations between sila
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Both strength and thermodynamic qua
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where Cand Dare constants for apart
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ThisisimportantwhenLCCCisappliedtoc
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Page 549 and 550:
Page 551 and 552:
However, strong adsorption of macro
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elution step may be sufficient for
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Figure 16 Block scheme of a full ad
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processing of 2D-HPLC data. Knowled
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Figure 20 Set of full retention-elu
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distributions of complex polymers a
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constituents were not discriminated
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(Sec. 7) and therefore they can be
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2. Identify sample solvents. First
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1 Segmental interaction energy para
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58. BG Belenkii. Pure Appl Chem 51:
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19 Methods and Columns for High-Spe
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Table 1 Summary of Methods for Incr
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not savealot of time and solvent, d
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Figure 3 Conventional SEC chromatog
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chromatogram at 4mL/min, which is f
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Sincethereductionoftheinternaldiame
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Table 3 Summary of Column Performan
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Figure 11 Dependence of column perf
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. Two-dimensional chromatography ru
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The standard deviations for the mol
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Figure 15 Comparison of time requir
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Figure 17 Accuracy and precision of
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polymer analysis. Samples are “ru
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just ignoring the fractionation of
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20 Automatic Continuous Mixing Tech
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out at low enough concentration tha
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educed viscosity, h r, to be comput
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Figure 2 Raw ACOMP signals from mul
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Figure 4 Mw vs. monomer conversion,
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decreases smoothly and monotonicall
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Figure 7 Effects of fluctuating rea
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Finally, the use of a light-scatter
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Figure 8 Linear and cubic increases
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where r(t) is now given by 2 6 r(t)
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Figure 11 Light scattering from sol
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3.1 ASimple System: Equilibrium Cha
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Figure 13 (a) ACM applied to the ch
Page 629 and 630:
Also of note in Fig. 13b is how hig
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15. JM Starita, CL Rohn. Rheologica
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52. M Hulden. Hydrophobically modif
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21 Light Scattering and the Solutio
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therefore, is to remove any lingeri
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is often found in the literature wh
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Figure 2 Configuration of an SEC se
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5 THE IMPORTANCE OF SOFTWARE Like a
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standard deviations of the measured
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These include the differential weig
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Figure 8 Data of Fig. 7corrected fo
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Figure 11 Data of Fig. 10 with spik
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Figure 13 Fitstodatacollectedatasli
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Table 1 Errors (in %) Characteristi
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homogeneous copolymer, that is, tak
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process may be used to identify the
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fractionated sample. They represent
Page 663 and 664:
Figure 16 An example of poor SEC ch
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on) methods, whereby the average di
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23. WH Stockmayer, LD Moore Jr, M F
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condition, as is explained in this
Page 671 and 672:
Figure 2 Partition coefficients KL
Page 673 and 674:
4 COLUMNS FOR HOPC Detailsaregiveni
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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
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Figure 10 SEC chromatograms for som
Page 685 and 686:
appropriate for the early fractions
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23 Size Exclusion/ Hydrodynamic Chr
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Figure 2 Calibration curve for the
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Figure 5 Elutionbehaviorofpolystyre
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Table 1 Comparison Between SEC and
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egular SEC column in which the pore
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Such an ideal separation can be obt
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