ANALYTICAL CHEMISTRY, VOL. 50, NO. 5, APRIL 1978 (391) J. D. R. Thomas, Proc. Anal. Div. Chem. Soc., 14, 7 (1977). (392) J. D. R. Thomas and G. J. Moody, Proc. Anal. Div. Chem. SOC., 12, 48 (1975). (393) R. C. Thomas, W. Simon and M. Cehme, Nature (London), 258, 754 (1975). (394) D. E. Thompson and R. S. Danchik, Anal. Lett., 8, 699 (1975). (395) S. L. Tong and G. A. Rechnitz, Anal. Lett., 9, 1 (1976). (396) K. Toth, G. Nagy, Z. Feher, and E. Pungor. Fresenius’ 2. Anal. Chem., 282, 379 (1976). (397) K. Toth and E. Pungor, Am. Lab., 8, 9 (1976). (398) I.Trachtenberg, Traces Heavy Met. Water Removal Processes Monit., Proc. Symp. 1973, J. E. Sabadell. Ed., NTIS, Springfield, Va. p 323. (399) K. T. Tran, Tap ChiHoa Hoc, 14, 25 (1976) (Vietnamese); Chem. Abstr., 86, 199369f (1977). (400) T. Treasure and D. M. Band, J . Med. Eng. Techno/.. 1. 271 (1977). (401) P. K. C. Tseng and W. F. Gutknecht, Anal. Lett., 9, 795 (1976). (402) P. K. C. Tseng and W. F. Gutknecht, Anal. Chern., 48, 1996 (1976). (403) A-M. Tsou, K-H. Chang, and H-C. Wang, Hua Hsueh Tung Pao(5), 299 (1976) (Ch.); Chem. Abstr., 86, 164721n (1977). (404) M. S. Turaeva and 0. 0. Lyalin, U.S.S.R. Patent 544899, Jan. 30, 1977; Appl. 1950 247, Aug. 3, 1973. (405) Y. I. Urusov, V. V. Sergievskii, A. Y. Syrchenkov, A. F. Zhukov, and A. V. Gordievskii, Zh. Anal. Khim., 30, 1757 (1975) (Russ.). (406) J. J. Vallon, Lyon Pharm., 26, 487 (1975) (Fr.). (407) R. E. Van De Leest, Analyst (London). 101, 433 (1976). (408) R. E. Van De Leest, N. M. Beekmans, and L. Heijne, German Patent 2600846, Aug. 19, 1976; Neth. Appl. 75/823, Jan. 24, 1975. (409) R. E. Van De Leest and L. Heijne, German Patent 2621 731, Dec. 9, 1976; Neth. Appl. 7516410, May 30, 1975. (410) M. A. Van den Heede, A. M. Heyndrickx, C. H. Van Peteghem, and W. A. Van Zele, J . Assoc. Offic. Anal. Chem., 58, 1135 (1975). (41 1) P. Van den Winkel, J. Mertens, T. Boel, and J. Vereecken, J , Nectrockm. Soc., 124, 1338 (1977). (412) J. M. Van der Meer, G. Den Boef and W. E. Van der Linden, Anal. Chim. Acta, 79, 27 (1975). (413) J. M. Van der Meer, G. Den Boef, and W. E. Van der Linden, Anal. Chim. Acta. 85. 317 (1976). (414) J. M. Van der Meer and J. C. Smit, Anal. Chim. Acta, 83, 367 (1976).
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(415) L. H. J. Van Kempen and F. Kreuzer, Natl. Bur. Stand(U.S.), Spec. Publ., 450, 239 (1977). (416) G. W. S. Van Osch and B. Griepink, Fresenius’ 2.Anal. Chem., 283. 29 (1977). (417) G. W.’S. Van Osch and B. Griepink, Fresenius’ 2 . Anal. Chem., 284, 267 (1977). (418) M. L. Verkhovskaya, E. S. Imasheva, G. A. Kurella, and L. G. Yaglova, Biol. Nauki(Moscow), 19. 142 (1976) (Russ.). (419) J. VeseM and J. Jicdra. Czech Patent 163358, Jun. 15, 1976; Appl. 68/5344 Jul. 22, 1968. (420) Y. G. Vlasov, I. V. Murin and E. A. Bichkov. Vestn. Leningrad Univ., 22, 129 (1975) (Russ.). (421) Y. G. Vlasov, A. L. Grekovich, E. A. Materova, I. V. Murin, and S. B. Kochereain. Ionnvi Obmen Ionometriva. 1. 170 11976) (Russ.). (422) Y. G-Vlasov, ‘S.B. Kocheregin, and’Y. E. Ermolenko, Elekrrokhimiya, 13, 109 (1977) (Eng.). (423) T. B. Warner, Phys. Chem. Sci. Res. Rep. 1975 l(Nat. Seawater, Rep. Dahlern Workshop 1975), 191. (424) B. Watson and P. J. Breno, U S Publ. Pat. Appl. B 51 1002, Mar. 6, 1976; Appl. 511 002, Oct. 1, 1974. (425) R. Wawro and G. A Rechnitz, J . Membr. Sci., 1, 143 (1976). (426) C. C. Westcott, Anal. Chim. Acta, 86, 269 (1976). (427) M. Whitfield, Proc. Anal. Div. Chem. Soc., 12, 56 (1975). (428) R. D. Wyvill, Prod. Finish. (London). 30, 21 (1977). (429) C.C. Young, U S . Patent 4 033 777 Jul. 5, 1977. Appl. 51 1 720, Oct. 3. 1974. (430) J. N. Zemel. Res./Dev., 28, 38 (1977). (431) J. N. Zemel, Anal. Chem., 47, 255A (1975). (432) M. S. Zetter, German Patent 2646314 May 5, 1977; U.S. Appl. 625857, Oct. 28. 1975. 1433) P.-L: Zhu. Hua Hsueh Tuna Pao. 15) 1Ch.l: , , 300 (1975) , , , Chem. Abstr.. ’ 84, 51371p (1976). (434) A. F. Zhukov, A. V. Gordievskii, V. S. Shterman, A. Y. Syrchenkov, and Y. I. Urusov, U.S.S.R. Patent 515984, May 30, 1976; Appl. 1939 127, Jul. 3. 1973. (435) A.F. Zhukov. A. V. Vishnyakov. Y. L. Kharif, Y. I. Urusov, F. K . Volynets, E.I. Ryzhikov, and A. V. Gordievskii, Zh. Anal. Khim., 30, 1761 (1975) (Russ.).
Gel Permeation Chromatography (Steric Exclusion Chromatography) V. F. Gaylor” The Standard Oil Company (Ohio), 4440 Warrensville Road, Cleveland, Ohio 44 128
H. L. James Waters Associates Inc., Maple Street, Milford, Massachusetts 0 1757
This review covers the time period of about December 1975 to November 1977. Since we depend on abstracting services in some cases, there is some time overlap with the period covered by the last review (73). The literature surveyed for this review included major analytical, chromatography, and polymer journals, as well as various abstracting services. We’ve included literature on size separation from soft gels (“gel filtration”), semi-rigid gels (“GPC”), and porous, inorganic column packings (“rigid gels”). And we‘ve reviewed size separations involving small molecules as well as work restricted to macromolecules. We continue to use the common abbreviation, GPC, for gel permeation chromatography applications involving all the above areas. The more definitive “steric exclusion chromatography” is, however, still preferred nomenclature.
GENERAL REVIEWS A number of books published during this period included one or more sections on theory and use of steric exclusion chromatography (28,55,152,174,176).Several review articles also included general GPC information. Abbott ( 1 ) and Miller (129) discussed elementary operating principles and usefullness for polymer analyses. Krauss and Krauss reviewed theory and practice of both thin layer and column GPC (105). Current status of aqueous GPC was reviewed by Cooper and 0003-2700/78/0350-029R$Ol . O O / O
Matzinger (40). Billmeyer reviewed trends in polymer characterization and discussed some of the limitations of GPC (24). A more general review discussed problems in optimizing high performance liquid chromatography (223),and correlations between GPC and affinity chromatography were included in a review of the latter subject (178).
LITERATURE SERVICES Bimonthly fact sheets summarizing current literature on gel permeation chromatography are now available from England (194). Preston Technical Abstracts Company issues monthly abstracts of current liquid chromatography literature (160), and Chemical Abstracts Service added High Speed Liquid Chromatography to the bimonthly CA Selects service (33); both of these series of abstracts include exclusion chromatography. A bibliography of 1971-73 literature on liquid chromatography was published as a supplementary volume to the Journal of Chromatograph3 (54). And a compilation of liquid chromatography data is now available from the American Society for Testing and Materials (8).
APPARATUS A bewildering array of high resolution liquid chromatographs is now marketed. McNair (128)reviewed requirements C 1978 American Chemical Society
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for the basic parts of a chromatograph, and listed features and specifications of instruments supplied by various manufacturers. A novel, and commercially available, microchromatograph was described by Karasek (93). This instrument uses micro-columns and flow rates as low as a few microliters per minute. Several claimed advantages, including lowered consumption of mobile phase, might be useful in the practice of exclusion chromatography. Advances in design of syringe pumps for high resolution liquid chromatography were reviewed (184). Achener et al. (2) discussed effects of solvent compressibility on operation of syringe pumps, and showed that well designed syringe pumps are satisfactory for quantitative work. A new, low volume, axial plunger pump with a trihead rotary cam plate was described (138). Van Lenten and Rothman (197) described a pressure control system applicable to any commercial pump, and evaluated use for pressure programmed supercritical fluid chromatography. An electro-pneumatic flow control system which controls flow rate to k0.370was described (13). Bly, Yau, and Stoklosa reported (27) that much of the error in high resolution GPC analyses caused by flow rate variations can be eliminated by using a syphon as a total volume counter; the total volume for a given analysis is used to calculate an accurate, average flow rate for use in calculations. A syphon type flow meter with a measurement precision similar to precision of high pressure pumps was described by Rossler, Schneider, and Halasz (166). And Wolkoff and Larose (206) devised a simple modification to a syphon volume counter to achieve accuracy in measuring flow rates of aqueous mobile phases. Two different, simple methods for thermostating columns with a water jacket were reported (142, 199). New syringe injection systems were described (171, 182), and Smith modified a sampling valve for syringe introduction of samples (179). Use of viscometric and light scattering detectors for molecular weight characterization of polymers increased, and examples of applications appear in other parts of this review. Scheinert improved accuracy of an on-line capillary viscometer by devising inlet tubes which prevented droplets of liquid entering the viscometer during efflux time measurement (172). Ouano automated the low-angle laser light scattering (LALLS) detector for GPC (147);computer assisted data acquisition and reduction eliminated most of the tediousness associated with using this very powerful pair of tools in tandem. Hoffmann and Urban used automated turbidimetric titration of GPC eluants to determine distributions of molecular weight and chemical compositions of binary linear copolymers (83). Post-column solute precipitation with light scattering measurement of the precipitated solute was also proved a very sensitive chromatographic detection method (91). Other detectors for liquid chromatography were reviewed (149),and advantages of variable wavelength UV detectors were discussed (190). Wise and May (205) reviewed unusual detectors for liquid chromatography; several of these newer detection systems could be useful in applying exclusion chromatography to nonpolymeric solutes. Several examples already exist. On-line atomic absorption detectors were used in exclusion chromatography analyses of organosilicon compounds (32) and condensed phosphates (209). Albaugh and Query used a Dohrmann microcoulometric sulfur analyzer to selectively measure size-separated sulfur-containing compounds in petroleum residuals ( 4 ) . The recently commercialized mass spectrometer interface for liquid chromatography is also intriguing. Though applications published to date (48, 127) do not include liquid exclusion separation examples, a mass spectrometer detector could be quite useful for some GPC applications. Design of a multichannel, hierarchical computing integrator for chromatography was described (115) and the future of microcomputer-based chromatographs was reviewed (43). Montoya and Leung discussed a multichannel chromatographic data system capable of molecular weight distribution data acquisition and reduction (136). Effects of digital filters on chromatographic data were quantitatively evaluated (42).
COLUMNS .4general review of recent advances in high performance liquid chromatography column packings included a survey of microparticulate rigid and semirigid packings for exclusion
chromatography (122),and Unger reviewed requirements for gel chromatography column packings (191). Dawkins and co-workers prepared and evaluated GPC performance of polystyrene gel fractions with average particle diameters ranging from 10 to 40 wm (52);they found, as expected, that column performance improved with decreasing particle size. Columns packed with particles less than 20 wm in diameter had plate counts greater than 3000 plates per foot. Krishen reviewed performance of high efficiency, small pore columns for separating small molecules (106) and showed that a difference of one carbon atom is sufficient for satisfactory resolution of lower molecular weight compounds (107,108). Significant advances were made in quality of rigid gels for exclusion chromatograpahy columns. Separation of monomers and low molecular weight oligomers on 6-11 Fm silica microspheres with 45-75 A pores was demonstrated (99). Several different methods of deactivating silica packings by bonding techniques were tested. Kirkland proposed trimethylsilyl modified porous silica for size separation of both macromolecules and small molecules (98). Engelhardt and Mathes characterized several different hydrophilic exclusion chromatography column packings prepared by chemically bonding various stationary phases onto porous silica (61). They showed that an amide-bonded column could be used with either dimethylformamide or water mobile phases. Vivilecchia et al. (200) illustrated use of ether modified silica for GPC use with both polar and nonpolar mobile phases. Silica modified with bonded alcohol hydroxyl groups was also shown applicable to aqueous GPC (192). Porous glass column packings deactivated with bonded glycerol were used for GPC study of water soluble polymers (25, 154), and Regnier and Noel covalently bonded a carbohydrate to porous glass for successful exclusion chromatography of proteins, nucleic acids, and polysaccharides (163). Several different new column packings were reported. Lindstrom et al. prepared spherical cross-linked lignin beads for packing GPC columns, and demonstrated separation of polystyrenes with dimethylformamide mobile phase ( 118). A new type of cellulose bead packing was prepared and found to be suitable for use in aqueous gel chromatography of polar compounds (156). Pertoft and Hallen formed silica-agarose beads by mixing agarose with colloidal silica ( I S ) , and found that the resulting column packing was mechanically stable at high pressures and high flow rates. A Spheron gel, prepared by copolymerization of 2-hydroxyethyl methacrylate with ethylenedimethacrylate, was evaluated for aqueous GPC (201). And Ansari and Mage found that Sepharose CL-EB is stable in the presence of strong denaturants and can be used for determining molecular weights of proteins (12). A polyurethane gel column was used with acetone mobile phase to separate ethylene glycol oligomers ( 112). Epton, Holding, and McLaren synthesized and characterized a poly(acryloy1 morpholine) gel and showed it to be a suitable GPC column packing for separating small molecules in water, chloroform, dimethylformamide, and pyridine mobile phases (63,64). The same type of column packing was also evaluated for the separation of protected peptides (72). Martin and Guiochon reviewed the various techniques used for packing microparticulate columns (124). New slurry packing methods used a combination of stirring to keep the particles floating and high initial pressure to transport the particles rapidly into the column (96,117). Upward packing of a dilute slurry was reported to have some advantages (29). Two different groups found that slurry packing with a pressurized CC14 medium produces good columns (41,204). Peterson developed an electropolishing method for polishing the interior surfaces of stainless steel tubing to produce improved columns (157). A simple, low dead volume end fitting for wide bore glass columns was described (30).
FUNDAMENTAL STUDIES Van Kreveld obtained identical results from two approaches to calculating excluded volume of linear macromolecules in GPC (196);both approaches used a one-dimensional description of a random coil molecule. Using narrow molecular weight distribution dextrans on controlled pore glass, Haller developed a data plotting procedure for deriving critical permeation pore size of the solutes studied; he found that critical permeation size thus derived corresponded to equivalent sphere diameters calculated from viscosity and
ANALYTICAL CHEMISTRY, VOL. 50, NO. 5 , APRIL 1978
V. F. Gaylor is Supervlsor of Chemical Analysis for the R&D division of The Standard Oil Company (Ohio) Ms Gaylor received her B S degree from Ohio University and an M S deoree from Western Reserve Universitv (now a part of Case Western Reserve University). She joined the Standard Oil Company (Ohio) immediately afler earning her B S and has since been employed in various phases of analytical chemistry in R&D Her scientific career has included analytical research and mthcd development in the areas of petroleum, petrochemicals, and synthetic polymers. She has authored and coauthored a number of papers in a number of disciplines which include polaroqraphy, qas chromatoqraphy, qas chromatoqraphy-mass spectrometry, petroleum analysis, trace analysis, and liquid exciusion- chromatography
m---
.
H. L. James Is a Technical Specialist with the Pdymer, phstics, and Energy Dwisim of Waters Associates, Inc., Houston office. Prior to joining Waters Associates, he was a chemist involved with polymer synthesis and characterization at the research facilities of General Tire and Rubber and Standard Oil of Ohio. Mr. James received his B.A. in chemistry from Syracuse University and his M.S. in polymer chemistry from the University of Akron. Currently a member of The American Chemical Society and Sigma Xi, he is also a co-editor of the ASTM Bibliography on Liquid Exclusion Chromatography.
ultracentrifuge measurements (80). An equation relating column packing pore size, molecular weight, and elution coefficient of monodisperse dextran was also derived (81). Casassa discussed t h e relation between a characteristic molecular dimension governing the exclusion phenomenon in relation to “universal” calibration in GPC (31);he concluded t h a t the product of intrinsic viscosity and molecular weight is not necessarily a common calibration factor for elution of all molecular species. Janca derived equations for quantitatively describing the processes leading to concentration dependence of elution volumes in the GPC behavior of polymers (84). A computational procedure for correcting polymer chromatograms for concentration effects was described (137). Rudin and Wagner developed a new model for correcting for concentration effects and for universal calibration for molecular weight determinations (167);the model provides useful predictions of the effects of concentration and solvent type on the effective hydrodynamic volumes of dissolved polymers. Bleha, Bakos, and Berek studied elution volume concentration dependence of polystyrene in various single and binary mobile phases and found that slope of the relationship depends on thermodynamic quality of the mobile phase (26). Their data supported interpretation of the GPC concentration effect as due to decreasing effective hydrodynamic volume with increasing polymer concentration, and suggested that concentration dependence could be used for estimating the second virial coefficient of the polymer-eluent system. Feurer and Gourdenne used a series of low molecular weight compounds to study effects of chemical structure on solvation and apparent size in GPC characteristics (66). Non-Exclusion Effects. Dubin briefly discussed nonexclusion, solute-gel interaction effects in exclusion chromatography (57). Dawkins considered behavior of polystyrenes chromatographed in various mobile phases on cross-linked polystyrene gel and suggested that solute-gel interaction effects are determined by the standard enthalpy change on solute transfer to the pore surface in the gel (50). Polystyrene adsorption studies on several different porous silicas were reported (601,and Kuzayev e t al. studied adsorption of glycol oligomers on silica as a function of mobile phase polarity (111). Ambler observed adsorption of poly(propylene oxide)glycol oligomers on Styragel columns and corrected peak elution volumes for this effect by extrapolating to “infinite concentration” ( 5 ) . Acetic acid was added to tetrahydrofuran mobile phase to suppress adsorption of
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terephthalic acid/ethylene glycol esters on cross-linked polystyrene gel (130). Non-exclusion separation effects for low molecular weight aromatic compounds on polystyrene gels were also reported (59, 140,159). Freeman and Killion used n-alkane probe molecules to study hydrocarbon interaction with a cross-linked polyacrylate gel as a function of mobile phase polarity (68),and suggested that partitioning effects may occur in most GPC fractionations. Sabbagh and Fagerson studied effects of operating variables on elution of glucose oligomers from polyacrylamide gel and concluded t h a t there were several separation mechanisms operating simultaneously (169). Effects of ionic strength on fractionation of poly(styrene sulfonates) on porous glass were reported (125). Urea addition to the mobile phase eliminated adsorption of protein-sodium dodecyl sulfate complexes on porous glass (70), and a n amino acid buffer was used to eliminate protein adsorption on the same type of column packing (135). Effects of operating variables on elution behavior of several different kinds of metallic compounds were also reported (53, 116, 187). Dubin e t al. studied non-exclusion effects in the GPC behavior of several different solutes from several stationary phases with a mobile phase of 0.01 M LiBr in dimethylformamide (58). Effects of LiBr on the GPC behavior of polyester-based polyurethanes (82) and polyimides (165) in dimethylformamide were also reported. Resolution. Unger and Kern reported a systematic study of effects of properties of silica packings on resolution in high performance GPC (193). Scott and Kucera tested exclusion properties of ten commercially available silica packings and demonstrated 250 000 theoretical plates for a microbore silica column (175). Effects of operating variables on efficiency of separating small molecules on semirigid gels were reported (71,189). Giddings et al. outlined procedures for identifying major contributions to plate height (75). The influence of extra-column band broadening on plate count was examined ( l o o ) ,and Knox and McLennan concluded that true plate height cannot generally be evaluated from a polymer standard with dispersity larger than about 1.01 (102). A resolution equation for gel chromatography was developed (92). Christopher proposed analyzing blends of monodisperse polystyrene standards as a method for evaluating performance of a GPC system and accuracy of analyses (35, 36). Yau e t al. developed a quantitative theory for interpreting the effect of packing pore size distribution on GPC performance and accuracy (207). Kat0 et al. showed that semirigid packings are now available for anal zing polystyrenes with molecular weights in the lo6 and 10 range (94). Band Spreading. Sorensen devised and tested an equation for the elution profile of a solute in a linear chromatographic system (180, 181);the expression includes a quasi-equilibrium term due to eddy diffusion in the column. A solution for the theory of chromatographic column operation a t intradiffusional kinetics of separation processes was offered (208). Two simplified methods for correcting for peak spreading in GPC were proposed (49,202). Basedow et al. tested several peak broadening correction methods and obtained good results for complicated chromatograms with several maxima (18). Ambler, Fetters, and Kesten showed that accurate molecular weights can be obtained without peak spreading correction with long column lengths and low flow rates (7). Kotaka used computer simulation to examine performance of a molecular weight monitored GPC, and showed that an LALLS detector does not eliminate the need for spreading correction (104). The same author proposed a simple method for calibrating columns for imperfect resolution (103). Anomalous results observed with GPC use of an automatic capillary viscometer were traced to zone spreading (85) and led to a method for direct determination of the resolution factor for the separation system employed (88). Grubisic-Gallot e t al. devised a technique for quantitatively evaluating the axial dispersion term from recycle GPC (76). Calibration. A new approach to calibrating GPC columns with polydisperse stand_ards was proposed (188). The method requires an Mn,M,,, or M, value for each of the standards used. Loy described a calibration-method _based on one polydisperse standard for which both M , and M , are known (120). Two different calibration methods were suggested by McCrackin (126). The first method uses polydisperse standards for which any molecular weight averages are known, but neglects peak
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ANALYTICAL CHEMISTRY, VOL. 50, NO. 5, APRIL 1978
spreading. The second method determines both calibration and spreading, but requires standards with fairly narro_w molec_ular weight distribution and known values for both M, and M , A simple method for GPC estimation of polypeptide chain lengths from calibration with three commercially available standards was described (162). Ogawa and Inaba studied deviations in calibration curves prepared from polydisperse polymers and improved analysis accuracy by fitting polynominals to nonlinear calibration curves (145). A simple method for calculating average molecular weights from chromatograms of copolymers containing variable proportions of ethylene and propylene was described (146). Dawkins roposed a new universal calibration equation containing t i e Mark-Houwink exponent as well as constants for the unperturbed dimensions (51). A simple method for developing a hydrodynamic volume calibration curve from polydisperse samples was described (121). The method requires intrinsic viscosity and average molecular weights for each of several polydisperse samples, as well as an M [ q ] universal calibration curve for another polymer. Kat0 et al. accurately measured average molecular weighta of chloroprene rubbers using only GPC, intrinsic viscosities of the unfractionated rubbers, and a polystyrene universal calibration curve (95). The h drodynamic volume universal calibration method was r o v e d applicable to chlorinated homopolymers and copo&ners (37,86, 164), polyacr lates (148,158,183), maleic anhydride copolymers (34, 170j', polybutadiene and poly(vinylacetate) (1501, isotactic polystyrene (771, cross-linked benzene) (161), carbanilate derivatives amylose (195). Additionally, Ambler showed that the universality of the M [ 7 ] calibration concept applies to oligomeric hydrocarbons with molecular weights as low as 100 ( 5 ) . Characterizations of commercially available polystyrenes used for GPC calibrations were reported (65, 87). A set of certified oly(vinylch1oride)reference materials were studied by GPC 6 4 ) . Preparation of polypropylene reference samples by preparative scale GPC was reported (198). Wagner and Hoeve studied the NBS standard polyethylene sample SRM 1475 and concluded that it is linear polymer (203). Sulfonated polystyrene calibration standards for aqueous GPC were synthesized and characterized (186).
TECHNIQUES B r a n c h i n g Studies. Scholte and Meijerink examined potentials of viscometric and light scattering measurements of GPC effluent for estimating branching in low density polyethylene and compared these techniques t o the DrottMendelson method (173). Ambler developed a modified method for determining branching in randomly branched polymers of all branching densities (6). This paper also proposed a method for predicting M [ 7 ] curves of branched polymers from M [ 7 ] calibration curves for linear polymers. An iteration method, based on deriving intrinsic viscosity of the whole polymer, was described for simultaneously estimating' number of branch points and average molecular weights from GPC data (109). Intrinsic viscosity-GPC methods were used to estimate long chain branching in poly(viny1 alcohol) (139) and polychloroprene (37). On-line viscometer detectors for GPC were used t o measure distribution of branching in low density polyethylene (1411, polybutadiene, poly(viny1 acetate), and poly(styrene/divinyl benzene) (151). Gel permeation chromatography analyses of a series of isomeric poly(ary1ene ether sulfones) showed presence of structural irregularities which may involve chain branching ( 1 5 ) . Bi and Fetters observed that GPC detected differences in the degree of branching in a series of styrene-diene star block copolymers (23). Bennett, Keller, and Stejny synthesized a low molecular weight hydrocarbon in order to study influence of molecular shape and branching on GPC elution volumes (20). P r e p a r a t i v e S c a l e GPC. Cooper et al. reviewed recent advances in, and applications of, preparative scale gel permeation chromatography (39). Process gel filtration was reviewed by Curling (45, 46). Three different gel packings were compared for prep-scale fractionation of coal liquids (38). Jones et al. used Sephadex LH-20 with three different mobile phases to obtain gram quantities of fractions of oils derived from coal and shale (90).Petroleum asphalts were fractionated on a 2-cm i.d. column packed with polystyrene gel (79).
Table I. References to Exclusion Chromatography Applications to Polymers Ref. Type of Polymer 1A-24A Polystyrenes 25A-49A Styrene copolymers 50A-56A Substituted styrene polymers 57A-61A Other aromatic polymers 6 2A-79A Diene polymers 80A-95A Polyethylene and polypropylene 96A-113A Methylmethacrylate polymers 114A- 123A Other acrylate polymers 124A-130A Other polyesters 131A-13 5A Ethylene and propylene oxide polymers 136A-140A Polyethers 14 1A-142A Polyurethanes 143A-145A Pol ylac tones 146A-151A Nitrogen heterocyclic polymers 152A-16 1A Halogen-containing polymers 162A-170A Phosphorous-containing polymers 171A-179A Silicon-containing polymers 180A, 181A Polysulfones Polyvinylferrocenes 182A, 183A Miscellaneous polymers 184A-188A 189A-213A Biochemical polymers Polyelectrolytes 2 14A- 220A Preparative scale GPC was also used to prepare narrow molecular weight fractions of cellulose trinitrate ( I 10) and lignosulfonate (67). Mirabella et al. used infrared analysis of prep-scale fractions to determine copolymer composition (132) and structure (131) of polymers as a function of molecular weight. Preparative scale GPC was also used to fractionate polybis(1-indenyl) (144), high molecular weight poly(viny1 chloride) (89), and poly(bis(mch1orophenoxy)phosphazene) (78). Lesec et al. used recycling GPC for semipreparative scale separation of diastereoisomers of acetal alcohols (114). A syringe-like sampling device for large sample injections was described (11). Other. Applications of chemical derivatization in the practice of liquid chromatography were covered in Volume 7 (113) in the Journal of Chromatography library of books devoted t o chromatographic techniques. Anderson et al. developed derivatization techniques for determining unsaturation distribution in diene copolymers (9) and functionality distribution in hydroxyl-terminated polybutadienes (10) by GPC. Several commercial polymers were analyzed by these derivatization/GPC methods (16). The distribution of fold-stem lengths in polyethylene was measured by GPC analysis of nitrated polymer (19). Paschke et al. developed a mixed mobile phase for room temperature GPC analysis of poly(ethy1ene terephthalate) (153); the new mobile phase is 0.5% nitrobenzene in tetrachloroethane. Slagowski et al. analyzed poly(tetramethy1ene terephthalate) using hexafluoroisopropanol as the GPC mobile phase (177). Berek et al. used GPC with a benzene-methanol mobile phase t o study preferential solvation of polystyrene (22). Preferential solvation of solute was also reported to be a source of host peaks in liquid chromatography (21). Eiddings, Bowman, and Myers proposed using fluids above normal boiling points as solvents for exclusion chromatography (74);advantages of reduced viscosity and increased speed were claimed. Use of pressure programming to improve separation of low molecular weight polystyrenes by supercritical fluid chromatography was demonstrated (101). Epstein designed an apparatus combining electrophoresis and gel filtration for continuous separation of macromolecules (62). Thin layer gel chromatography was shown to be a good tool for rapid, simultaneous assessment of large numbers of protein coupling reactions (97). Crouzet and Martens developed general software for resolving peaks in complex GPC chromatograms of ethylene and propylene oxide adducts (44). Gel filtration chromatography was used t o study Donnan equilibria (119). Bartick and Johnson used differential GPC t o determine concentration dependence of hydrodynamic dimensions (17). Freeman and Poinescu used solutes of known size to characterize pore structure of GPC column packings (69).
A N A L Y T I C A L CHEMISTRY, VOL. 50, NO.
Table 11. References to Exclusion Chromatography Applications to Small Molecules
Analyte Oils, pitches, etc. Additives in polymers Degradation products of polymers Monomers in polymers Aromatic oligomers Other cyclic oligomers Miscellaneous oligomers
Ref. 2 21A- 2 27 A 2 28A- 2 30A 231A, 232A 2 33A- 2 3 5A 236A-243A 24 4 A- 2 4 8A 249A-2 5 3 A
Stop-and-go GPC/IR was shown useful for qualitative analyses of polymers and additives (133)and for determining copolymer composition as a function of molecular weight ( 1 3 4 ) . Nesterov et al. separated silver colloids containing both ionic and colloidal particles by GPC (143). A mathematical model for simulating hydrodynamic chromatography performance, and for calculating particle size distributions, was reported (185).
APPLICATIONS A separate bibliography of applications is appended. Table I lists references t o use of exclusion chromatography for characterizing polymers. References to applications to small molecules are tabulated in Table 11. LITERATURE CITED Gel Permeation Chromatography
(1) Abbott, S. D., Am. Lab., 9 (e), 41 (1977). (2)Achener, P., Abbott, S. R., Stevenson, R. L., J . Chromatogr., 130,29 (1977). (3) Adam, G. A., Haward, R. N., Parsons, I. W.. Eur. Polym. J . , 12,279 (1976). (4) Albaugh, E. W., Query, R. C., Anal. Chem., 48, 1579 (1976). (5) Ambler, M. R., J . Polym. Sci., Polym. Lett Ed., 14,683 (1976). (6) Ambler, M. R., J . Appl. Polym. Sci., 21, 1655 (1977). (7) Ambler, M. R . , Fetters, L. J., Kesten, Y., Ibid., 21, 2439 (1977). (8) American Society for Testing and Materials, "Liquid Chromatographic Data Compilation", Atomic and Molecular Data Series 41. (9) Anderson, J. N., J . Appl. Polym. Sci., 18,2819 (1974). (10) Anderson, J. N., Baczek, S. K., Adams, H. E., Vescelius, L. E., ibid., 19, 2255 (1975). (1 1) Andreotti, R. E., U.S. Patent 3 826 373 (1974). (12) Ansari, A. A., Mage, R. G., J . Chromatogr., 140,98 (1977). (13) Asai, K., Kanno, Y., Nakamoto, A. Hara, T., lbid., 128, 369 (1976). (14) Atkinson, C. M., Dietz, R., Polymer, 18,408 (1977). (15) Attwocd, T. E., King, T., McKenzie, I. D., Rose, J. B., ibid., 18,365 (1977). (16)Baczek, S. K., Anderson, J. N., Adams, H. E., J . Appl. Polym Sci., 19, 2269 (1975). (17) Bartick, E. G.,Johnson, J. F., Polymer, 17,455 (1976). 118) Basedow, A.M., Ebert, K. H., Ederer, H., Hunper, H., Makromol. Chem., 177, 1501 (1976) (19) Bassett, D C , Khalifa, B A , Oliey, R H I J Polym S o , Polym Phys Ed 15 995 (19771 (20) Bennett. R i..Keiier. A.. Steinv. J.. J . Polvm. S a . . Polvm Chem E d . 14,3021 (1976) (21) Berek, D , Bleha, T I Pevna, 2 , J Chromatogr S c i , 14, 560 (1976) (22) Berek, D Bieha, T I Pevna, 2 , J Pokm Scl , Polym Left E d , 14,323 119761 (23j Bi?-L-K,,Fetters, L. J., Macromolecules, 9! 732 (1976). (24) Billmeyer, F. W., Jr., J . Polym. Sci., Polym. Symp., 55, 1 (1976). (25) Blagrove, R. J., Frenkel, M. J., J . Chromatogr., 132,399 (1977). (26) Bleha, T., Bakos, D., Berek, D., Polymer, 18,897 (1977). (27) Bly, D. D., Yau, W. W., Stoklosa, H. J., Anal. Chem., 48, 1256 (1976). (28) Brlstow. P. A., "Liquid Chromatography in Practice", 10 Langley Drive Handforth, Wllmslow, Cheshire SK9 380, United Kingdom, 1976. (29)Bristow, P. A., BrHtain, P. N., Riley, C. M., Williamson, 8. F., J. Chromfogr., 131, 57 (1977). (30) Cantweii, F. F., Anal. Chem., 48, 2044 (1976). (31) Casassa, E. F., Macromolecules, 9, 162 (1976). (32)Cassidy, R. M., Hurteau, M. T., Misian, J. P.,Ashley, R. W., J , Chrometogr. Sci., 14,444 (1976). (33)Chemical Abstracts Service, P.O. Box 3012,Columbus, Ohio 43210,"CA .
I
Selects: High Speed Liquid Chromatography".
(34) Chow, C. D., J . Appi. Polym. Sci., 20, 1619 (1976). (35) Christopher, P. C.. ibid.. 20, 2989 (1976). (36) Chrlstopher, P. C., /bid., 21, 871 (1977). (37)Coleman, M. M., Fuller, R. E., J , Macromol. Sci., Phys., 11. 419(1975). (38)Coleman, W. M., Wooton, D. L., Dorn, H. C., Taylor, L. T., Anal. Chem., 49,533 (1977). (39) Cooper, A. R., Hughes, A. J., Johnson, J. F., Chromatographia, 8, 136 (1975). (40) Cooper, A. R., Matzinger. D. P., Am. Lab., 9 (l),13 (1977). (41) Cos, B., Gonnet, C., Rocca, J. L., J , Chromatogr., 108, 249 (1975). (42) Cram, S. P., Chesler. S. N., Brown, A . C., 111, ibid., 126,279 (1976). (43) Crockett, I. L., Mikkeisen, L., J . Chromatogr. Sci., 14, 169 (1976). (44) Crouzet, P., Martens, A. J., Chromatographia, 8,675 (1975). (45) Curling, J., Am. Lab., 8 ( 5 ) ,47 (1976). (46) Curling, J., lbid., 8 (6),31 (1976).
5, APRIL 1978
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(47)Danheika. J., Kossler. I., Bohackova. V.. J . Polym. Sci., Polym. Chem. Ed., 14, 267 (1976). (48) Dark, W. A., McFadden, W. H., Bradford, D. L., J . Chromatogr. Sci., 15, 454 (1977). (49) Dawidowicz, A., Sokolowski, S . , J . Chromatogr., 125,428 (1976). (50) Dawkins, J. V., J . Polym. Sci., Polym. Phys., Ed., 14, 569 (1976). (51) Dawkins. J. V., Eur. Poiym. J . , 13,837 (1977). (52) Dawkins, J. V., Stone, T., Yeadon, G., Polymer, 18, 1179 (1977). (53) Deguchi, T., J , Chromatogr., 120, 159 (1976). (54) Deyl, Z., Kopecky, J., "Bibliography of Liquid Column Chromatography 1971-1973",Supplementary Volume No. 6, 1976,to J . Chromatogr. (55) Deyi, Z.,Macek, K., Janak, J., "Liquid Column Chromatography", J . Chromtogr. Library,Vol. 3,Elsevier Scientific Publishing Company, Amsterdam and New York.
(56)Drushel, H. V., Prepr., Div. Pet. Chem., Am. Chem. SOC.,20 (Z),146 (1975). (57) Dubin, P. L , Ind. Res., 18,(7),55 (1976). (58) Dubin. P. L., Koontz, S..Wright, K. L.. 111. J . Polym. Sci., Poly. Chem. Ed., 15, 2047 (1977). (59) Einarsson, R.. Zeppezauer, M., J . Organomet. Chem., 71,277 (1974). (60) Eitekov, Y. A,, Nazansky, A. S., J . Chromatogr., 116,99 (1976). (61) Engelhardt, H., Mathes, D.. ibid., 142,311 (1977). (62) Epstein, I., Chromatographia, 10,65 (1977). (63) Epton, R . , Holding, S. R.. McLaren. J. V., Polymer, 17, 843 (1976). (64)Epton, R., Hoiloway, C., Mclaren, J. V., J Chromatogr., 117,245 (1976). (65) Fetters, L. J., J . Appl. Polym. Sci., 20,3437 (1976). (66)Feurer, B., Gourdenne, A., Prepr., Div. Polym. Chem., Am. Chem. Soc., 17 (2),459 (1976). (67)Forss, K. G., Steniund, B. G., Sagfors, P.-E., J . Appl. Polym. Sci., Appl. Polym. Symp., 28, 1185 (1976). (68) Freeman, D. H., Killion, D., J . Polym. Sci., Polym. Phys. Ed., 15,2047 (1977). (691 Freeman, D. H., Poinescu. I. C., Anal. Chem., 49, 1163 (1977). (70) Frenkei, M. J., Blagrove, R. J., J , Chromatogr., 111. 397 (1975). (71) Fujita, I . , Arikawa, I . , Anai. Instrum. 1974 Suppi., 101 (1974). (72) Gaipin, I. J., Handa, B. K., Kenner, G. W., Moore, S., Ramage, R., J . Chromatogr., 123, 237 (1976). (73)Gaylor, V. F., James, H. L., Weetail, H. H., Anal. Chem., 48,44R (1976). (74) Giddings, J. C., Bowman, L. M., Jr., Myers, M. N., /bid., 49,243 (1977). (75)Giddings, J. C., Bowman, L. M., Jr., Meyers, M. N., Macromolecules, 10, 443 (1977). (76)Grubisic-Gailot, Z., Marais, L., Benoit, H.. J . Polym. Sci., Poly. Phys. Ed., 14,959 (1976). (77)Guenet, J. M., Gallot, 2.. Picot, C., Benoit. H., J . App;. Polym. Scl., 21, 2181 (1977). (78)Hagnauer, G. L., LaLiberte, B. R., J . Polym. Sci., Polym. Phys., Ed., 14, 367 (1976). (79) Haiey, G. A., Anal. Chem., 47, 2432 (1975). (80) Haller, W., Macromolecules, 10,83 (1977). (81)Haller, W., Basedow, A. M., Konig, B., J . Chromatogr., 132,387 (1977). (82) Hann, N. D., J . Poiym. Sci., Poly. Chem. Ed., 15, 1331 (1977). (83) Hoffmann, M., Urban, H., Makromol. Chem., 178,2683 (1977). (84) Janca, J., J . Chromatogr., 134,263 (1977). (85) Janca, J., Kolinsky, M., ibid., 132, 187 (1977). (86) Janca, J., Kolinsky, M., J . Appl. Polym. Sci., 21,83 (1977). (87)Janca, J., Kolinsky, M., Mrkvickova, L., J . Chromatogr., 121,23 (1976). (88) Janca, J., Pokorny, S.,/bid., 134, 273 (1977). (89) Jisova. V.. Janca. J.. Koiinskv. M.. J , Polvm. Sci.. Polvm. Chem. Ed.. i 5 , 533 (1977). (90)Jones, A. R., Guerin, M. R . , Clark, E. R., Anal. Chem., 49, 1766 (1977). (91) Jorgenson, J. W., Smith, S.L., Novotny, M., J . Chromatogr., 142,233 119771. (92j Kaiasz, H., Magyar, K., Barnes, W. T.. ibid., 128,300 (1976). (93) Karasek, F. W., ResJDev., 28 (l),42 (1977). (94)Kato. Y.. Kametani. T., Hashimoto. T.. J , P o l m . Scl.. Polvm. Phvs. Ed.. 14,2105 (1976). (95)Kato, Y., Takamatsu, T., Fukutomi, M., Fukuda, M., Hashimoto, T., J . Appl. Polym. Sci., 21, 577 (1977). (96) Kelier, H. P., Erni, F., Llnder, H. R., Frei, R. W., Anal. Chem., 49, 1956 (1977). (97j Kennedy, J. H., Kricka, L. J., Wilding, P., J . Chromatcgr., 118,337 (1976). (98) Kirkland, J. J., ibld., 125, 231 (1976). (99) Kirkland, J. J., Antle, P. E., J . Chromatogr. Sci., 15, 137 (1977). (100) Klrkiand, J. J., Yau. W. W., Stokiosa, H. J., Diiks, C. H., Jr.. lbid., 15, 303 (1977). (101)Kiesper, E., Hartmann, W., J. Polym. Sci., Polym. Len. Ed., 15,9 (1977). (102) Knox, J. H., McLennan, F., Chromatographia, 10, 75 (1977). (103) Kotaka, T., Angew. Makromol. Chem., 56, 77 (1976). (104) Kotaka, T., J . Appl. Polym. Sci., 21, 501 (1977). (105) Krauss, G. J., Krauss, G., Wiss. Fomchr., 24, 126 (1974). (106) Krishen, A . , J . Chromatogr. Sci., 15,434 (1977). (107) Krishen, A., Tucker, R. G., Anal. Chem., 49, 898 (1977). (108) Krishen, A., Tucker, R. G., ibid., 49, 1647 (1977). (109)Kurata, M., Okamoto, H., Iwama, M.. Abe, M.. Homma. T.. Rubber Chem. Technoi., 49, 1290 (1976). (110)Kusama, Y., Kageyama, E., Shimada, M., Nakamura, Y., J . Appl. Polym. Sci.. 20. 1679 (1976). (111)Kuzayev, A. i., Mirontseva, G. A , Olkhova, 0. M., Enteiis, S. G., Zh. Fiz. Khim, 48, 1235 (1974):Chem. Abstr., 61, 111761~(1974). (112)Kuzayev, A. I., Suslova, Y . N., Entelis, S . G., "Gel-Pronikayushch. Khromat., Chernogoiovka"; Chem Abstr.. 83,28987q (1975). (113) Lawrence, J. F., Frei, R. W., "Chemical Derivatization in Liquid Chromatography", J. Chromtogr. Library, Vol. 7,Elsevier Scientific Publishing Company, Amsterdam and New York.
(114) Lesec, J., Lafuma, F.. Quivoron, C., J , Chromatogr., 138, 89 (1977).
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A N A L Y T I C A L CHEMISTRY, VOL. 50, NO. 5, APRIL 1978
(115) Leung, A. T., Hubbard, J. R., Miller, L. A., J. Chromafogr. Sci., 14, 166 (1976). (116) Limoni, B., Schmuckler, G., J. Chromatogr., 135, 173 (1977). (117) Linder. H. R., Keller. H. P., Frei, R. W., J. Chromatour. Sci., 14, 234 (1976). (118) Llndstrom, T , Soremark, C., Westman, L., J. Appl. Polym. Sci., 21, 2873 (19771 (1 19, L%tdsirom, T.. DeRuvo, A,, Soremark, C., J. Polym. Sci., Polym. Chem. Ed.. 15. 2029 (1977). (120) LOY, 8. R.. 'ibid,,'l4,2321 (1976). (121) Mahabadi, H. K., O'Driscoll, K. F., J. Appl. Polym. Sci., 21, 1283 (1977). (122) Majors, R. E., J. Chromafogr. Sci., 15, 334 (1977). (123) Martin, M., Eon, C., Guiochon, G., ResJDev., 26 (4), 24 (1975). (124) Martin, M., Guiochon, G., Chromatographla, 10, 194 (1977). (125) Matzinger, D. P., Cooper, A. R., Prepr., Div. Polym. Chem., Am. Chem. SOC., 17 (2), 450 (1976). (126) McCrackin, F. L., J, Appl. Polym. Sci., 21, 191 (1977). (127) McFadden, W. H., Bradford, D. C., Games, D. E., Gower, J. L., Am. Lab., 9 (IO),55 (1977). (128) McNair, H. M., Chandler, C. D., J. Chromafogr. Sci., 14, 477 (1976). (129) Miller, B., Plast. World, 34 (2), 44 (1976). (130) Minarik, M., Sir, Z.,Coupek, J., A q e w . Makroml. Chem., 64, 147 (1977). (131) Mirabelia, F. M., Jr., Barrail, E. M., 11, Johnson, J. F., J. Appl. Polym. Sci., 20, 765 (1976). (132) Mirabelh, F. M., Jr., Barrall, E. M., 11, Johnson, J. F., ;bid., 20, 959 (1976). (133) Mirabella, F. M., Jr., Barrail, E. M., 11, Johnson, J. F., Polymer, 17, 17 (1976). (134) Mirabella, F. M., Jr., Barrall, E. M., 11, Jordon, E. F., Jr., Johnson, J. F., J. Appl. Polym. Sci., 20, 581 (1976). (135) Mizutani, T., Mizutani, A.. J . Chromafogr., 111, 214 (1975). (136) Montoya, E. F., Leung, A. T., Am. Lab., 8 (6). 53 (1976). (137) Mori. S..J . Aool. Polvm. Sci.. 20. 2157 (1976). (138j Mori, S.,Mochiiuki, K , Watanabe, M., Saito, M.;Am. Lab., 9 ( l o ) , 21 (1977). (139) Morishima, Y.. Kim, W., Nozakura. S., Polymer J., 8, 196 (1976). (140) Nakae, A., Muto, G.. J. Chromatogr., 120, 47 (1976). (141) Nakano, S., Goto, Y., J . Appl. Polym. Scl., 20, 3313 (1976). (142) Nelson, J. A., Rose, L. M., J. Chromatogr., 106, 188 (1975). Nefedov, P. P., Talmud, (143) Nesterov, V. V., Belenkii, B. G., Sokolova, B. I., S. L., Kolloid. Zh.. 37, 1184 (1975); Chem. Abstr., 84, 50267x (1976). (144) Nicolet, P., J. Macromol. Sci., Chem., 11 (3), 577 (1977). (145) Ogawa, T., Inaba, T., J. Appl. Polym. Sci., 20, 2101 (1976). (146) Ogawa, T., Inaba, T., ibid., 21, 2979 (1977). (147) Ouano, A. C., J. Chromatogr., 118, 303 (1976). (148) Ouano, A. C., Dawson, B. L., Johnson, D. E., Prepr., Div. Polym. Chem., Am. Chem. Soc., 17 (2), 925 (1978). (149) Pajurek, J., Krejci, M., Jemna Mech. Opt., 19, suppl. to No. 6-8, 11, and 12 (1974). (150) Park, W. S.,Graessley, W. W.. J. Polym. Sci., Polym. Phys. Ed., 15, 71 (1977). (151) Park. W. S., Graessley. W. W., ibid., 15, 85 (1977). (152) Parris, N. A., "Instrumental Liquid Chromatography", J. Chromatogr. Library, Vol. 5 Elsevier Scientific Publishing Company, Amsterdam and New York. (153) Paschke, E. E., Bidlingmeyer, B. A., Bergmann, J. G., J. Polym. Sci., Polym. Chem. Ed., 15, 983 (1977). (154) Persiani, C., Cukor, P., French, K., J. Chromatogr. Sci., 14, 417 (1976). (155) Pertoft, H., Hallen. A,, J. Chromatogr., 128, 125 (1976). (156) Peska. J.. Stambera. J.. Hradil. J.. Ilavskv. M.. ibid.. 125. 455 119761. . . i i 5 7 j Peterson, H. B., J.-Chromatogr. sci., 14, 211 (1976). (156) Pittman, C. U., Jr., Hirao, A,, J. Polym. Sci., Polym. Chem. Ed., 15, 1677 (1977). (159) Popl, M., Fahnrich, J., Stejskal, M., J. Chromatogr. Sci., 14, 537 (1976). (160) Preston Technical Abstracts Company, P.O. Box 312, Niles, Ill. 60648. "Abstracts of Liquid Chromatography Literature". (161) Price, C., Forget, J.-L., Booth, C., Polymer, 18, 526 (1977). (162) Rao, N. V., Adams, E., Anal. Biochem., 68, 209 (1975). (163) Regnier, F. E., Noel, R., J. Chromatogr. Sci., 14, 316 (1976). (164) Revillon. A., Dumont, B., Guyot, A., J. Polym. Sci., Polym. Chem. Ed., 14, 2263 (1976). (165) Richard, M.. Gourdenne, A., PreDr., Div. Polym. Chem., Am. Chem. Soc., 17 (2),464 (1976). (166) Rossler, G., Schneider, W., Halasz, I., Chromafographia, 6. 237 (1973). (1671 Rudin. A.. Waaner. R. A,. J. Aool. Polvmn. Sci.. 20. 1483 11976). i168j Rier,'J., Magogch, K.-H., Feinaue;, R., Ahgew. Makro&ol. Chem., 56, 139 (1976). (169) Sabbagh, N. K., Fagerson, I.S.. J. Chromatogr., 120, 55 (1976). (170) Samuels. R. J.. Polymer, 18, 452 (1977). (171) Schaufele, G., Feder. Rep. Germany Pat. No. 2026329 (1974). (172) Scheinert, W., Angew. Makromol. Chem., 63, 117 (1977). (173) Scholte, T. G., Meljerink, N. L., J., Br. Polym. J., 9, 133 (1977). (174) Scott, R. P. W., "Contemporary Liquid chromatography", John Wiley & Sons, New York, N.Y., 1976. (175) Scott, R. P. W., Kucera, P., J . Chromatogr., 125, 251 (1976). (176) Simpson, C. F., "Practical High Performance Liquid Chromatography", Heyden & Son Ltd., London, England, 1976. Sci.. 11771 Siaaowski. E. L.. Gebauer.. R. C... Gaesser.. G. J... J. ADD/. Polvm. , 21, 2253 (1977). (178) Shvik, K., Chem. Listy. 69, 339 (1975); Chem. Abstr., 83, 39553w (1975). (179) Smith, S. C., Anal. Chem., 48, 2045 (1976). (180) Sorensen, T. S., J. Chromatogr., 68, 197 (1974). (181) Sorensen, T. S.,Acta Chem. Scand., Ser. A, 28, 753 (1974). (182) Spaans, H., Terol, H., Onderwater. A., J. Chromafogr. Sci., 14, 246 (1976). (183) Stejskal, J., Janca, J., Kratochvii, P., Polymer J., 8, 549 (1976). (184) Stevenson, R. L., J. Chem. Educ., 53 (2), A82, A95, A96, A98, A104 (1976).
..
~
(185) Stoisits, R. F., Poehlein, G. W., Vanderhoff, J. W., J. ColloidInferface Sci., 57, 337 (1976). (186) Sutheriand, J. E., Prepr., Div. Polym. Chem., Am. Chem. Soc., 17 (2). 434 (1976). (187) Suzuki, N., Saitoh, K., Shibukawa. M., J . Chromatogr.. 138, 79 (1977). (188) Szewczyk, P.. Polymer, 17, 90 (1976). (189) Takai, N.. Yamabe. T., Seisan Kenkyu, 26, 278 (1974); Chem. Abstr., 81. 1 4 5 4 1 4 ~11974). (lSO)'Thomas, H. L., h d . Res., 19 ( l ) , 57 (1977). (191) Unger, K., Chimia, 28, 679 (1974); Chem. Abstr., 82, 22114k (1975). (192) Unger, K., Becker, H., Kramer, E., Chromatographla, 8, 283 (1975). (193) Unger, K., Kern, R., J . Chromafogr., 122, 345 (1976). (194) United Kingdom Chemical Information Service, Nottingham NG7 2RD, "Macroprofile Fact Sheet-Gel Permeation Chromatography". (195) Van Dijk, J. A. P. P., Henkens, W. C. M., Smit, J. A. M., J. Polym. Scl., Polym. Phys. Ed., 14, 1485 (1976). (196) Van Kreveid. M. E., bid., 13, 2253 (1975). (197) Van Lenten, F. J., Rothman, L. D., Anal. Chem., 48, 1430 (1976). (198) Vaughan, M. F., Francis, M. A., J. Appl. Polym. Sci., 21, 2409 (1977). (199) Vigh, G., J. Chromatogr., 117, 424 (1976). (200) Vivilecchia, R. V., Lightbody, B. G., Thimot, N. Z.,Quinn, H. M., J. Chromatogr. Sci., 15, 424 (1977). (201) Vondruska, M., Sudrich, M., Mhdek, M., J. Chromatcgr., 116, 457 (1976). (202) Vozka, S., Kubin, M., ibid., 139, 225 (1977). (203) Wagner, H. L., Hoeve, C. A. J., J. Polym. Sci., Polym. Symp., 54, 327 (1976). (204) Webber, T. J. N., McKerrell, E. H., J. Chromatogr., 122, 243 (1976). (205) Wise, S. A,, May, W. E., Res./Dev., 28 (IO) 53 (1977). (206) Wolkoff, A. W., Larose, R. H., J. Chromatogr. Sci., 14, 51 (1976). (207) Yau, W. W., Kirkland, J. J., Bly, D. D.. Stoklosa, H. J., J. Chromatogr., 125, 219 (1976). (208) Yelkin, G. E., Lebediev, Y. Y . , Samsonov, G. V., Vysokomol. Soyedin, 17, 1870 (1975); Chem. Abstr., 83, 1688592 (1975). (209) Yoza, N., Kouchiyama, K., Miyajima, T., Ohashi, S.. Anal. L e f t , 8, 641 (1975). Gel Permeatlon Chromatography Appllcatlons (1A) Abbas, K. B., Porter, R. S., J. Polym. Sci., Polym. Chem. Ed., 14, 553 (1976). (2A) Benoit, H., J. Macromol. Sci., Phys., B I Z , 27 (1976). (3A1 Dunbar, J. I., North, A. M., Pethrick, R. A,, Steinhauer, D. B., J. Polym. Sci., Polym Phys. Ed., 15, 263 (1977). (4A) Fukano, K , Kageyama, E.. J. Poly. S c i , Polym. Chem. Ed., 14, 1743 11976) > - -, (5A) Fukano, K., Kageyama, E., ;bid., 14, 2193 (1976). (6A) Fukutomi, T., Toyoura, M., Kakurai, T., Polymer J., 6, 174 (1976). (7A) Goodail, A. R., Wilkinson, M. C., Hearn, J.. J. Polym. Sci., Polym. Chem. Ed., 15, 2193 (1977). (8A) Hoffmann, M., Makromol. Chem., 177, 1021 (1976). (9A) Hsieh. H. L.. J. Polvm. Sci.. Polv. . . ' Chem. Ed.. 14. 379 (1976). (lOA) Ito, K., ibid., 15. 507 (1977). (1 1A) Kamide, K., Miyazaki, Y., Abe, T., Makromoi. Chem.. 177, 485 (1976). (12A) Kleintjens, L. A., Koningsveld, R., Stockmayer, W. H., Br. folym, J . , 8. 144 (1976). -, (13A) Koszterszitz, G., Schulz, G. V., Makromol. Chem., 178, 1149 (1977). (14A) Masuda, T., Sawamoto, M., Higashimura, T., ;bid., 177, 2981 (1976). (15A) Merle, G., Pascauil, J. P., Pham, Q. T., Pillot, C., Saile, R., Gole, J., Rashkov, I., Panayotov, I., Guerard, D., Herold, A., J . Polym. Sci., Polym. Chem. Ed., 15, 2067 (1977). (16A) Murakami, K., Nakanishi, H., ibid., 14, 489 (1976). (17A) Pinazzi, C., Lenain, J.-C., Brosse, J.-C., Eur. Polym. J., 12, 529 (1976). (18A) Roovers, J. E. L., Polymer, 16, 827 (1975). (19A) Sawamoto, M., Masuda, T., Higashimura, T., Makromol. Chem., 177, 2995 (1976). (20A) Sawamoto, M., Masuda, T.. Higashimura, T., ibid., 178, 1497 (1977). (21A) Sawamoto, M., Masuda, T., Higashimura, T., Kobayashi, S., Saegusa, T., ibid., 178, 389 (1977). (22A) Shultz, A. R., Mankin, G. I., J. Polym. Sci.. Polym. Symp., 54, 341 (1976). (23A) Snyder, C., McIver, W., Sheffer, H., J. Appl. Polym. Scl., 21, 131 (1977). (24A) Takaki, M., Asami, R., Ichikawa, M.. Macromolecules. 10, 850 (1977). (25A) Abadie, M.. Burgess, F. J., Cunliffe, A. V., Richards, D. H., J . Polym. Sci., Polym. Leff. Ed.. 14, 477 (1976). (26A) Allen, P. E. M., Chiaramonte, P., Hunter, L. J., Mair, C.. Williams, E. H., J. Polym. Sci., Polym. Symp., 55, 231 (1976). (27A) Burgess, F. J.. Cunliffe, A. V., Richards, D. H.,Sherrington, D. C., J. Polym. Sci.. Polym. Left. E d . , 14, 471 (1976). (28A) Corbin, N., Prud'homme, J., J. Polym. Sci., Polym. Chem. Ed., 14, 1645 (1976). (29A) Cunliffe, A. V., Hayes, G. F . , Richards, D. H., J. Polym. Sci., Polym. Leff. Ed., 14, 483 (1976). (30A) Feinberg, S. C., Kennedy, J. P., Prepr., Div. Polym. Chem., Am. Chem. Soc., 17 (2), 797 (1976). (31A) Fukano, K., Kageyama, E., J. Polym. Sci., Polym., Chem. Ed., 14, 2183 (1976). (32A) Funt, B. L., Paweichak, G. A., ibid., 14, 2639 (1976). (33A) Higashimura, T., Yamamoto, K., ibid., 15, 301 (1977). (34A) Hrdlovic, P.. Danecek, J., Berek, D., Lukac, I., Eur. Polym. J.. 13, 123 (1977). (35A) Kawai, W., J. Polym. Sci., Polym. Chem. Ed., 15, 1479 (1977). (36A) Kilp, T., Guillet, J. E., Macromolecules, 10, 90 (1977). (37A) Krause, S.,Dunn, D. J., Seyed-Mozzaffari, A,, Biswas, A. M., ;bid., 10, 786 (1977). (38A) Lovric, L., Grubisic-Gallot, Z., Kunst, B., Eur. Polym. J., 12, 189 (1976). (39A) Nakamura, K., Endo, R., Takeda, M., J. Polym. Sci., Polym. Phys. Ed., 14, 135 (1976). (40A) Nakamura, K., Endo, R . , Takeda, M., ibid., 14, 1287 (1976). ~
~
A N A L Y T I C A L CHEMISTRY, VOL. 50, NO. 5, APRIL 1978 (41A) Omichi, H., Araki, K., J . Polym. Sci., Poly. Cbem. Ed., 14,2773 (1976). (42A) Pinazzi, C., Fernandez, A., Makromol. Cbem., 177,3089 (1976). (43A) Podesva, J., Bohdanecky, M., Kratochvil, P., Samay, G., J . Polym. Sci., Polym. Pbys. Ed., 15, 1521 (1977). (44A) Rahlwes, D., Roovers, J. E. L., Bywater, S., Macromolecules, IO. 604 (1977). (45A) Sakota, K., Okuno, K., Okaya, T., Tsuchiya, S.,J . Appl. Polym. Sci., 20, 2811 (1976). (46A) Shiraishi, S., Seno, M., Ishii, M., Asahara, T., ibid., 20, 2429 (1976). (47A) Terrell, D. R., Katiofsky. H., ibid., 21, 1311 (1977). (48A) Toporowski, P. M., Roovers, J. E. L., J . Polym, Sci., Polym. Cbem. Ed., 14, 2233 (1976). (49A) Trathnigg, B., Junek, H., Angew. Makromoi. Cbem., 5 3 , 81 (1976). (50A) Bareiss, R. E., Bellldo, J., Makromoi. Cbem., 177,3571 (1976). (51A) Berry, G. C., b g e r , B. L., Wong, C.-P., Macromlecules, IO, 361 (1977). (52A) Gibson, H. W., Bailey, F. C., bid., IO, 602 (1977). (53A) Higashimura, T., Kishiro, O., Takeda, T., J . Polym. Sci., Polym. Cbem. Ed., 14, 1089 (1976). (54A) Lenz. R. W., Westfelt, L. C., ibid., 14, 2147 (1976). (55A) Leonard, J., Malhotra, S. L., J . Macromi. Sci. Cbem., IO, 1279 (1976). (56A) Yamamoto, Y., Irie, M., Hayashi, K., Polymer J . , 8, 437 (1976). (57A) Cais. R. E.. Bovev. F. A,. Macromolecules. IO. 752 (1977). i58Aj Garreau, H., Marechal, E., Eur. Polym. J . , 13,29 (1977). (59A) Phillips, D. C., Davies, D. H., Smith, J. D. B., Spewock, S., J , Poiym. Sci., Polym. Cbem. E d . , 15, 1563 (1977). (60A) Stolka, M., Yanus, J. F., Pearson, J. M., Macromolecules,9,710 (1976). (61A) Stolka. M.. Yanus. J. F., Pearson, J. M.. ibid., 9,715 (1976). (62A1 Ambler. M. R.. J . A m i . Poivm. Sci.. 20. 2259 11976). (63Aj Campos-Lopez, E., An'guio-Sanchez, J. L., J , Po/ym Sci., Polym Lett. Ed., 14. 649 (1976). (64A) Cheng, T. C., Halasa, A. F., J . Polym. Sci., Polym. Cbem. Ed., 14,563 11976). (65A) Churb'aeva, L. A,, Valuev, V. I., Dmitrieva. T. S.,Lobach, M. I., Sokolov, V. N., Shlyachter, R. A., Kormer, V. A., Macromolecules. 9, 214 (1976). (66A) Cowan, J. R., Hammond, J. M., Hooper, J. F., J . Polym. Sci., Polym. Symp., 55, 17 (1976). (67A) Davidjan, A., Nikoiaew, N., Sgonnik, V., Belenkii, B., Nesterow, V., Erussalimsky, B., Makromol. Cbem., 177, 2469 (1976). (68A) Douy, A., Jouan, G., Gallot, B., ibid., 177,2945 (1976). (69A) Foss, R. P., Jacobson, H. W., Sharkey, W. H., Macromolecules, IO, 287 (1977). (70A) George, M. H.. Hayes, G. F., Makromol. Cbem.. 177, 399 (1976). (71A) Giurco, F.. Mills, W., J . Polym. Sci., Polym. Symp., 55, 25 (1976). (72A) Halasa, A. F., Mitchell, G. B., Stayer, M., Tate, D. P., Oberster, A. E., Koch, R. W., J . Polym. Sci., Poly. Cbem. Ed., 14,497 (1976). (73A) Hsieh. H. L., Rubber Cbem. Tecbnol.. 49, 1305 (1976). . . (74A) Morita, E.. ibid., 49, 1019 (1976). (75A) Perly, B., Douy, A.. Gallot. B., Makromoi. Cbem., 177, 2569 (1976). (76A) Rabek, J. F., Ranby, B., J . Polym. Sci., Polym. Cbem. Ed., 14, 1463 (1976). (77A) Smith, B. R., Rubber Cbem. Tecbnol., 49, 278 (1976). (78A) Sonnenfeld, R . J., J . Appl. Polym. Sci., Appl. Polym. Symp., 26,51 (1975). (79A) Yamashita, S., Kohjiya, S.,Atomori, S., Yamada, A., Angew. Makromoi. Cbem.. 56, 65 (1976). (80A) Bersted, B. H., J . Appl. Polym. Sci., 20, 2705 (1976). (81A) Capaccio, G., Crompton, T. A., Ward, I. M., J . Polym. Sci., Polym, Pbys. Ed., 14, 1641 (1976). (82A) Chakraborty. K. B., Scott, G.. Eur. Polym. J , , 13, 731 (1977). (83A) Handlos, V. N., Singer, K. A.. J . Appi. Polym. Sci., 20,3375 (1976). (84A) Havakawa. N.. Kurivama. I..J . Polvm. Sci.. Poivm. Cbem. Ed.. 14. 1513 (i976) (85A) Hlnschberger, A , Welll, A , Tarnat, J Angew Makromoi Cbem , 56, 121 (1976) \ . - . ( 8 6 4 Holtrup, W., Makromoi. Cbem., 178, 2335 (1977). (87A) Hosemann. R., Cackovic, H., Loboda-Cackovic, J., /bid., 176,3065 (1975). (88A) Luft, G., Lindner, A,, Angew. Makromol. Cbem., 56, 99 (1976). (89A) Machon, J. P., Eur. Poiym. J . , 12, 805 (1976). (90A) Mortimer. G. A., J . Appi. Polym. Sci., 20, 55 (1976). (91A) Nakagawa, K., J . Polym. Sci., Polym. Cbem. Ed., 14, 1293(1976). (92A) Olley, R. H., Bassett, D. C., J . Polym. Sci., Polym. Pbys. Ed.. 15, 1011 (1977). (93A) Rhein, R. A,, Ingham, J. D., Polymer, 16,799 (1975). (94A) Shiono, T., Niki, E., Kamiya, Y., J . Appl. Polym. Sci., 21, 1635 (1977). (95A) Saga, K., Izumi, K., Ikeda, S., Keii, T., Makroml. Chem., 178,337 (1977). (96A) Barson, C. A., Ensor, R., Eur. Polym. J . , 13, 113 (1977). (97A) Carlblom, L. H., Pappas. S. P.. J . Polym. Sci, Polym. Cbem. Ed., 15, 1381 (1977). (98A) Casale, A., Moroni, A,, Civardi, E., Angew. Makromoi. Cbem., 53, 1 (1976). (99A) Fukano, K., Kageyama, E., J . Polym. Sci., Polym. Cbem. Ed., 14, 1031 (1976). ( l o o n ) Fukano, K.. Kageyama, E., ibid., 14,275 (1976). (101A) Freilich. Y. L.. Levy, M.. Reich, S.,ibid.. 15. 1811 (1977). (102A) Hay, J. N., Roy, S.,Eur. Polym. J . , 13, 1 (1977). (103A) Lai, J. H., J . Appi. Polym. Sci., 21, 847 (1977). (104A) Lai, J. H., Shepherd, L., ibid., 20, 2367 (1976). (105A) Ouano, A. C., Johnson, D. E., Dawson, B., Pederson, L. A., J . Polym. Sci., Polym. Cbem. E d . , 14, 701 (1976). (106A) Paul. S., Ranby, B., ibid., 14, 2449 (1976). (107A) Pinazzi. C., Lenain, J.-C., Brosse, J.-C., Legeay, G., Makromol. Cbem., 177, 3139 (1976). (108A) Rossi, J., Gallot, B., ibid.. 177, 2801 (1976). (109A) Schnabel, W., Sotobayashi, H., Polymer J . , 8, 423 (1976). ( l l O A ) Tavel. P., Rufenacht, H. J., Makromol. Cbem.. 177, 2431 (1976). (111A) Viswanathan, N. S., J. Polym. Sci., Poiym. Cbem. Ed., 14,1553(1976). I
,
- I
35R
(112A) Warzelhan, V., Schuiz. G. V., Makromol. Cbem., 177,2185 (1976). (113A) Yamaguchi. T., Ono, T., Saito, Y., Ohara, S., Angew. Makromi. Chem., 53, 65 (1976). (114A) Cardenas, J . N., O'Driscoll, K. F., J . Polym. Sci., Polym. Cbem. Ed., 15,2097 (1977). (115A) Donnelly, E. F., Johnston, D. S.,Pepper, D. C., Dunn, D. J., J . Polym. Sci., Polym. Lett. Ed., 15,399 (1977). (1 16A) Hadjichristidis, N., Makromoi. Cbem., 178, 1463 (1977). (117A) Hillman. D. E., Lindley, H. M., Paul, J. I.. Pickles, D., Br. Polym. J . , 7, 397 (1975). (118A) Logothetis, A. L., McKenna, J. M., J . Polym. Sci., Polym. Cbem. Ed.. 15, 1441 (1977). (119A) Niezette, J., Hadjichristidii,N., Desreux, V., Eur. Polym. J., 13,41 (1977). (120A) Niezette, J., Hadjichristidis, N., Desreux, V., Mskromoi. Cbem., 177, 2069 (1976). (121A) North, A. M., Pethrick, R. A., Phillips, D. W., Polymer, 18,324 (1977). (122A) Probst, J., Kolb, G., Makromol. Cbem., 177, 2681 (1976). (123A) Wunderlich, W., ibid., 177,973 (1976). (124A) Ast. W., Rheinwald, G., Kerber, R., ibid., 177, 1349 (1976). (125A) Burns, R., Gandhi, K. S.,Hankin, A. G., Lynskey, B. M., Piast. Polym., 43, 230 (1975). (126A) Heitz, W., Henke, G., Platt, K.-L., Bier, P., Angew. Makromol. Cbem., 63,203 (1977). (127A) MatSUmOtO. A., Inoue, I., Oiwa, M., J . Polym. Sci., Polym. Cbem. Ed.. 14, 2383 (1976). (128A) Matsumoto, A., Yokoyama, S., Khono, T., Oiwa, M., J . Polym. Sci., Polym. Pbys. Ed., 15, 127 (1977). (129A) Pinazzi. C , Lenain, J.-C., Brosse, J.-C., Legeay, G.. Makromoi. Cbem., 177. 2861 (1976). (130A) Yokawa, M,', Ogo, Y., bid., 177, 429 (1976). (131A) Ashman, P. C., Booth, C., Polymer, 17, 105 (1976). (132A) Cassidy, R. M., Niro, C. M., J . Cbromatogr., 126, 787 (1976). (133A) Hartley, A. J., Leung. Y. K., McMahon, J.. Booth, C., Shepherd, I.W., Polymer, 18, 336 (1977). (134A) Ishigaki, I . , Morishita, N., Morita, Y . , Ito, A., J . Appi. Polym. Sci., 21. 749 (1977). (135A) Maclaine, J. Q.G., Ashman, P. C.. Booth, C., Polymer, 17, 109 (1976). (136A) Croucher, T. G., Wetton, R. E., ibid., 17, 205 (1976). (137A) Kunitake, T., Takarabe, K., Tsugawa, S.. Polymer J . , 8, 363 (1976). (138A) Kuzayev, A. I., Olkhova, 0. M., Entelis, S. G., Vysokomoi. Soyedin., 17, 2120 (1975); Cbem. Abstr., 83,206700a (1975). (139A) Lopata, E. S.,Riccitiello, S.R., J . Appl. Polym. Sci., 21, 91 (1977). (140A) Malhova, S.L., Leborgne, A,, Blanchard, L. P., J . Macroml. Sci., Chem.. 11, 603 (1977). (141A) Dearlove, T. J., Campbell, G. A., J . Appl. Polym. Sci., 21, 1499 (1977). (142A) Shibatani, K., Lyman, D. J., Shieh, D. F., Knutson, K., J . Polym. Sci., Polym. Cbem. E d . , 15, 1655 (1977). (143A) Hamitou, A., Ouhadi, T., Jerome, R., Teyssie, R., ibd., 15,865 (1977). (144A) Iida. M., Araki, T., Teranishi, K., Tani, H.. Macromolecules, IO, 275 (1977). (145A) Ouhadi, T., Stevens, C., Teyssie, Ph., J . Appi. Polym. Sci., 20,2963 (1976). (146A) Bevington, J. C., Dybail, C. J., J . Polym. Sci., Polym. Cbem. Ed., 14, 1819 (1976). (147A) Griffiths, C. H.. VanLaeken, A., J . Polym. Sci., Polym. Pbys. Ed., 14, 1433 (1976). (148A) Senogks, E., Thomas, R., J. Polym. Sci., Polym. Symp., 55. 241 (1976). (149A) Tanikawa, S.,Enomoto, T., Hatano, M., Motegi, K., Okuno. Z., Makromi. Cbem., 176,3025 (1975). (150A) Turner, S. R., Stolka, M., Prepr., Div. Polym. Cbem., Am. Cbem. Soc., 17 (2), 602 (1976). (151A) Wilson, J. C., J . Polym. Sci., Polym. Cbem. Ed., 14, 2927 (1976). (152A) Abbas, K. B., Sorvik, E. M., J . Appl. Polym. Sci., 20, 2395 (1976). (153A) Griffiths, C. H., Okumura. K., Van Laeken, A,, J . Polym. Sci., Polym. Pbys. Ed., 15. 1627 (1977). (154A) Kaifayan, S. H., Silver, R. H.. Liu, S. S., Rubber Cbem. Tecbnol.. 49, 1001 1976). (155A) Kuo, J., Lenz, R. W., J . Polym. Sci., Poiym. Cbem. Ed., 14, 2749 (1976). (156A) Laverty, J. J., Gardlund, 2. G., hid., 15, 2001 (1977). (157A) Lawson, D. F., J . Appl. Polym. Sci., 20, 2183 (1976). (158A) Lukas, R., Kolinsky, M., J . Polym. Sci., Polym. Cbem. Ed., 14,403 ( 1 976). (159A) Lyngaae-Jorgensen, J., J . Appl. Polym. Sci., 20, 2497 (1976). (160A) Rabek, J. F., Canback, G., Lucky, J., Ranby. B., J . Polym. Sci.. Polym. Cbem. Ed., 14, 1447 (1976). (16lA) Ver Strate, G.. Baldwin, F. P., Prep., Div. Polym. Cbem., Am. Cbem. Soc., 17 (2), 808 (1976). (162A) Allcock, H. R., Fuller, T. J., Mack, D. P., Matsumura, K., SmeRz, K. M., Macromolecules. IO. 824 11977). (163A) Azuma, C., MacKnight: W. J:, J . Polym. Sci., Polym. Cbem. Ed., 15, 547 (1977). (164A) Busulini. L.. Oselbme, M.,Lora, S.. Pezzin, G., Makromol. Cbem., 178, 277 (1977). 165A) Carlson, D. W., O'Rourke, E., Valaitis, J. K., Altenau, A. G., J . Polym. Sci., Polym. Cbem. Ed., 14, 1379 (1976). 166A) Dieck, R. L., Goldfarb, L., ibid., 15,361 (1977). 167A) Hagnauer. G. L., LaLiberie, B. R., J. Appl. Polym. Sci., 20,3073 (1976). 168A) Kajiwara, M., Nakashima, K., Saito, H., J . Macromol. Sci., Cbem., 11, 449 (1977). 169A) Pechkovskii, V. V., Cherches, G. Kh., Kuzmenko, M . I . , UspekbiKbimii, 44, 172 (1975); Cbem. Abstr., 82, 1 4 8 8 9 9 ~(1975). 170A) Yoza, N., Ishaibashi, K., Ohashi, S., J . Cbromatogr., 134,497 (1977). 171A) Hedaya, E.. Kawakami, J. H., Kopf, P. W., Kwiatkowski, G. T., McNeil, D. W., Owen, D. A,, Peters, E. N., Tulis, R. W., J . Polym. Sci., Polym. Chem. Ed., 15, 2229 (1977).
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1978
(172A) Lee. C. L., Johannson, 0. K., ibid., 14. 729 (1976). (173A) Llauro, M. F., Bartholin, M., Guyot, A,, lbid., 15, 1869 (1977) (174A) Mandik, L., Kotlanova, A., Fohn. J., C k m . Prum., 26, 87 (1976); C k m . Abstr., 84. 180757t (1976). (175A) Nametkin, N. S., Semenov, 0. B., Durgarian, S. G., Skazka, V. S., Filippova, V. G., Nikolayev, V. Ya., Vysokomol. Soyedin., 17, 973 (1975); Chem. Abstr., 83, 79836x (1975). (176A) Okui, N., Magiil, J. H., Polymer, 17, 1086 (1976). (177A) Pacansky, T. J., Prepr., Div. Polym. Chem., A m . Chem. Soc., 17 (2), 564 (1976). (178A) Peters, E. N., Stewart, D. D., Bohan, J. J., Moffitt, R., Beard, C. D., Kwiatkowski, G. T., Hedaya, E., J , Polym. Sci., Polym. Chem. Ed., 15, 973 ( 1977). (179A) Pittman, C. U., Jr., Patterson, W. J., McManus, S. P., ibid., 14, 1715 (1976). (180A) Cais, R. E., Bovey, F. A., Macromolecules, 10, 757 (1977). (181A) Gipstein, E., Moreau, W., Chiu, G.. Need, 0. U., 111, J . Appl. Po/ym. Sci., 21, 677 (1977). (182A) George, M. H., Hayes, G. F.. J . Polym. Sci., Polym. Chem. E d . , 14. 475 (1976). (183A) Smith, T. W., Kuder, J. E., Wychick, D., ibid., 14, 2433 (1976). (184A) Booth, R. G., Cooper, A. R., Prepr., Div. Polym. Chem., Am. Chem. Soc., 17 (2). 473 (1976). (185A) Gugliemelli, L. A,, Swanson, C. L., Doane. W. M., Russell, C. R., J . Appl. Polym. Sci., 20, 3175 (1976). (186A) Okada, M., Sumltomo, H., Irii, S., Makromol. Chem., 177, 2331 (1976). (187A) Roylance, D. K., DeVries, K. L., Prepr., Div. Polym. Chem., Am. Chem. Soc., 17 (2), 720 (1976). (188A) Zucconi, T. D., Humphrey, J. S., Polym. Eng. Sci., 16, 11 (1976). ( l 8 9 A ) Broido, A., Yow, H., J . Appl. Polym. Sci., 21, 1667 (1977). (190A) Broido, A., Yow, H., ibid., 21, 1677 (1977). (191A) Epton, R., Marr, G., Morgan, G. J., Polymer, 18, 319 (1977). (192A) Erins, P., Cinite, V., Jakobsons, M., Gravitis, J., J . Appl. Polym. Sci., Appi. Polym. Symp., 28, 1117 (1976). (193A) Fishman, M. L., Anal. Biochem., 74, 41 (1976). (194A) Franek, M., Hruska, K. J., J . Chromatogr., 119, 167 (1976). (195A) Harada, A., Furue, M,, Nozakura, S., Macromolecules, 9, 701 (1976). (196A) Heidemann, E., Neiss, H. G., Khodadadeh, K., Heymer, G., Sheikh, E. M., Saygin, O., Polymer, 18, 420 (1977). (197A) Heymer, G., Heidemann, E. R., Makromol. Chem., 177, 3299 (1976). (198A) Kainuma, K., Nogami, A., Mercier, C., J . Chromatogr., 121, 361 (1976). (199A) Koshijima, T., Yaku, F., Tanaka, R., J . Appl. Polym. Sci.,Appl. Polym. Symp., 28, 1025 (1976). (200A) Kupec, J., Stranel, O., Vondruska, M., Mladek, M., Ziklik, A,, Bosan, Z., Chem. Listy, 69, 752 (1975); Chem. Abstr.. 84, 1 1 1 1 8 7 ~(1976). (201A) Lundquist, K., J . Appl. Polym. Sci., Appl. Polym. Symp., 28, 1393 (1976). (202A) Macritchie, F.. J . Poiym. Sci., Polym. Symp., 55, 139 (1976). (203A) Miyatake, R., Kumanotani, J., Makromol. Chem., 177, 2749 (1976). (204A) Noble, A. C., J . Agric. Food Chem., 24, 321 (1976). (205A) Omura, I . , Lee, D. C., Itou, S.,Teramoto, A., Fujita, H., Polymer, 17, 847 (1976). (206A) Onishi, S.,Fujikake, M., Ogawa. Y., Ogawa, J., Birth Defects, Orig. Artic. Ser., 12, 41 (1976): Chem. Abstr.. 88, 10271213 (1977). (207A) Salak, J., Roch, P., Palousova, Z., J . Chromatogr., 107, 234 (1975). (208A) Sinner, M., Parameswaran, N., Yamazakl, N., Liese, W., Dletrichs, H. H., J . Appl. Polym. Sci., Appl. Polym. Symp., 28, 993 (1976). (209A) St. John Manley, R., lbid., 28, 693 (1976). (210A) Sugisaka, N., Petracek, F. J., Fed. Proc., Fed. Am. SOC.Exp. Blol., 38, 89 (1977); Chem. Abstr., 88 67140q (1977). (211A) Uwu. T.. Tachlkawa. H.. Ohaku. K.-I.. Terui. K.. Matsuiski. K.. Makrotnol, ‘ Ckem.; 178, 1929 (1977). (212A) Wlnston, A,, McLaughlin, 0. R., J . Polym. Sci., Polym. Chem. Ed., 14, 2155 (1976). (213A) Wu, A. C. M., Bough, W. A., Conrad, E. C., Aiden, K. E . , Jr., J . Chromatogr., 128, 87 (1976).
(214A) Drobnik. J.. Kopecek, J., Labsky, J., Rejmanova. P., Exner, J.. Saudek. V., Kalal, J . , Makromol. Chem.. 177, 2833 (1976). (215A) Dubin, P., Prepr., Div. Polym. Chem., Am. Chem. Soc., 17 (2), 341 (1976). (216A) Hofreiter, 8. T., J . Appl. Polym. Sci., 21, 761 (1977). (217A) Huglin, M. B., Johnson, 8 . L., Richards, R. W., J . Polym. Sci., Polym. Chem. Ed., 14, 1363 (1976). (218A) Kopecek, J., Makromol. Chem,, 178, 2169 (1977). (219A) Vejrosta. J., Malek, J., J . Chromatogr., 109, 101 (1975). (220A) Peppas, N. A., Merrill, E. W.. J . Polym. Sci., Polym. Chem. E d . , 14, 459 (1976). (221A) Bennett, R. L., Keller, A., Stejny, J., Murray, M., ibid., 14, 3027 (1976). (222A) Coupek, J., Pokorny, S.,Mares, E., Zezulkova, L. Luan, N.-T.. Pokorny, J., J . Chromatogr., 120, 411 (1976). (223A) Cunningham, A. F., Furneaux, G. C., Hillman, D. E., Anal. Chem., 48. 2192 (1976). (224A) Holasova, M., Blattna, J., J . Chromarogr., 123, 225 (1976). (225A) Lewis, 1. C., Petro, B. A., J . Polym. Sci., Polym. Chem. Ed., 14, 1975 (1976). (226A) Oren, J. J., MacKay. G. D. M., IP 76-005, Institute of Petroleum, 61 New Cavendish St., London. WIM 8AR, U.K. (227A) Sanborn, D. M., Winer, W. O., Prepr., Div. Pet. Chem., Am. Chem. S O C . , 21 ( l ) , 57 (1976). (228A) Hata. N., Kumanotani, J.. J . Appl. Polym. Sci., 21. 1257 (1977). (229A2) Rotschova-Protivova, J.. PosDisiI. J., Holcik. J.. Durmis. J., J. Chromatoqr., 106, 343 (1975). (230A) TSUII, T , Nakao, K , J Adhes SOC , Jpn , 10, 169 (1974); Chem Abstr , 84 , 6048c (1976) .~.~ - ~, (231A) Crouzet, C.. Marchal, J., Makromol. Chem., 177, 2819 (1976). (232A) Kolomeyer, M. G., Vainshtein, E. F., Entelis, S. G., Gel-Pronikayush. Khromat., Chernogolovka, USSR, 1974, 123 (1974); Chem. Abstr., 82, 171653n (1975). (233A) Nowlin, T. E., Boyd., W. H., J . Polym. Sci., Polym. Chem. Ed.. 14, 2341 (1976). (234A) Spagnolo, F., Malone, W. M., J . Chromatogr. Sci., 14, 52 (1976). (235A) Takeuti, T., Morisada, T., Anal. Instrum., 1974 Suppl., 159 (1974). (236A) Asanuma, T., Yamamoto, M., Nishijima, Y., J . Polym. Sci., Polym. Left. E d . , 15, 89 (1977). (237A) Braun, D., Lee, D. W., Angew. Makromol. Chem., 51, 11 (1976). (238A) eassie, N., Schoff, C., Cunningham, J. G., Eur. Polym. J . 12, 647 (1976). (239A) Higashimura, T., Nishii, H., J , Polym. Sci., Polym. Chem. Ed., 15, 329 (1977). (240A) Hocker, H., Lattermann, G., J , Polym. Sci.. Polym. Symp., 54, 361 (1976). (241A) Kronstadt, M., Tyburczy, J. A,, Dubin, P. L., Prepr., Div. Polym. Chem., A m . Chem. Soc., 17 (2), 446 (1976). (242A) Teder, Y. T.. Lippmaa, Kh. V., Kaps, T. K., Kijsler, K. R., T r . Taliln. Poiitekhn. Inst., 1974, 69 (1974); Chem. Abstr., 83, 98237u (1975). (243A) Wentworth, S. E.,Macaione, D. P., J . Polym. Sci., Polym. Chem. Ed., 14, 1301 (1976). (244A) Hocker, H., Reimann, W., Riebel, K., Szentivanyi, Z.,Makromol. Chem., 177, 1707 (1976). (245A) Ito, K.. Hashizuka, Y., Yamashita, Y., Macromolecules. 10, 821 (1977). (246A) Kawakami. Y., Yamashita, Y . , ibid., 10, 837 (1977). (247A) Leborgne, A., Malhotra, S. L., Blanchard, L.-P., J . Polym. Sci., Polym. Chem. Ed., 14, 2853 (1976). (248A) Van Craeynest, W. M., Goethals, E. J., Eur. Polym. J., 12, 859 (1976). (249A) Dankeiman, W., Daemen, J M. H., deBreet, A. J. J., Mulder, J. L., Huysmans, W. G.B., dewit, J., Angew. Makromol. Chem., 54, 187 (1976). (250A) Friday, A., Cooper, D. R., Booth, C., Polymer, 18, 171 (1977). (251A) Novak, J., Bleha, M., Coupek, J., Angew. Makromol. Chem., 84, 187 (1977). (252A) Novak, J., Bleha; M., Votavova, E., Coupek, J., J . Chromatogr., 130, 141 (1977). (253A) Rhee, C.-K., Ferry, J. D., Fetters, L. J., J . Appl. Polym. Sci., 21, 783 (1977). \
Ion Exchange and Liquid Column Chromatography Harold F. Walton Department of Chemistry, University of Colorado, Boulder, Colorado 80309
This review spans the time from the 1976 review to the journals available to t h e author on December 31, 1977. I depended heavily on the new “CA Selects” in high-speed liquid chromatography, along with a “Dialog” computer-based reference search in ion-exchange separations. Together, these lists gave well Over 2000 references. I wanted to keep the bibliography to 500 items. The selection was arbitrary as usual, but preference was given to new materials and methods. 0003-2700~78/0350-036R$050010
Many applications are cited, but they are illustrative, not exhaustive. The reader who wants a list of’ all papers on amino acids, for example, should order his own computer search. Preference was given to publications accessible to readers in English-speaking countries. Paper and thin-layer chromatography are not included in this review, nor is size-exclusion chromatography, save for two references to “hydrodynamic chromatography”. “Affinity ‘? 1978 Amer can Chemioal Society
