氧化铝及改性氧化铝高效液相色谱的制备和性能评价
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摘要
与SiO_2相比较而言，金属氧化物特别是ZrO_2和Al_2O_3在色谱性能上具有
很大的互补性，在某些物理化学性质上还具有一定优势。但ZrO_2的孔结构不够
理想，Al_2O_3的改性困难在很大程度上限制了它们在高效液相色谱中作为固定
相的应用。针对这两个问题，本论文进行了如下工作：
（i）用溶胶—凝胶法制备了ZrO_2—Al_2O_3复合氧化物填料，研究了氧化物微
球的孔结构、孔径、孔容、比表面积、表面耐碱性，并用β-氨基乙膦酸对其进行了
改性，系统地研究了改性ZrO_2-Al_2O_3的正相色谱性能。考察了流动相性质和组
成对溶质的保留行为的影响和酸性、碱性、中性化合物在改性ZrO_2—Al_2O_3上的
色谱行为。
芳香族化合物在该固定相的HPLC保留行为表明：采用吸附法对ZrO_2—
Al_2O_3复合氧化物的改性是可行的。该固定相表现出一些氨基键合硅胶固定相
类似的色谱性能：对酚的保留较强，对芳烃的保留较弱；一些芳香胺化合物的容
量因子的对数与极性溶剂在流动相中的比例的对数成良好的线性关系。
（ii）用酸腐蚀法制备了Al_2O_3固定相，以不同的流动相评价了其正相色谱性
能，考察了酸性、碱性、中性化合物在Al_2O_3固定相上的色谱行为。酸性化合物的
保留较强，部分酸性化合物出现不可逆吸附；碱性化合物保留适中，峰形较为对
称，中性化合物保留甚弱。上述的色谱保留行为说明在Al_2O_3表面存在有
Bronsted酸性中心和Lewis酸性中心。
（iii）利用Al_2O_3表面存在的Lewis酸性中心，用Lewis碱β-氨基乙膦酸对
Al_2O_3进行了改性，用二元流动相评价了其色谱性能，并与Al_2O_3固定相的色谱
性能进行了比较。
结果表明：Lewis酸性中心已被β-氨基乙膦酸覆盖，酸性化合物得以洗脱，
但峰形仍旧不好。中性化合物的保留行为与在Al_2O_3固定相上的保留亦有所不
同，部分碱性化合物的分离选择性得到了提高。
（iv）制备了β-环糊精改性Al_2O_3固定相，以苯及萘的衍生物考察了β-环糊
精改性Al_2O_3的色谱性能，并与相同条件下β-氨基乙膦酸改性Al_2O_3的色谱性
卜奎氯J巧士学上论丈
＼‘。、。。、。／．二二二于＜丁、厂二，口
能进行了比较，分析了卜环糊精改性AI0。固定相的保留机制：溶质分子在尺寸
上与卜环糊精的匹配程度、氢键的形成都影响着溶质的保留。部分对映异构体
在卜环糊精改性川o。固定相上得到了较好的分离。
Metal Oxides, especially zirconia and alumina have been found to be
complementary column packing materials of silica for High ?Performance
Liquid Chromatograph,both of them even showing some advantages of physico
hemical properties over silica. However their applicabilities are often limited
by the poor pore structure of zirconia and the difficulty of modifying alumina
surface. The purposes of our studies are to improve the pore structure of
zirconia and to make the modification of alumina easy and effective.
The main researchs and conclusions in this thesis are as follows:
(i)Zirconialurnina particles were prepared by the sol-gel process. Most
physical properties of them such as pore structure, particle size and specific
surface area were studied. The particles were then modified with 13-aminoethyl
phosphoric acid and served as a new stationary phase. whose chromatographic
performance was evaluated by using ethanol ?oyelohexane, chloroform ?
oyclohexane as mobile phase.
The distinctive chromatographic behaviors of some aromatic compouds on
the modified columm of Zr02-A1203 and the columm of Zr02-A1203 indicated
that it was practable for Zr02-A1203 to be modified with f3-
aminoethylphosphoric acid. Basic compounds such as pyridine~ aniline and
derivatives of them had symmetrical peaks, with poorly shaped peaks of
phenols and polyeyclic aromatie hydrocarbons (PAHs) absorbed poorly on the
modified stationary phase. The logk of some derivatives of aniline had a good
linear relationship with the content of eluent in the mobile phase.
(ii) The particles of alumina were prepared by acid erosion. The
chromatographic performance of the column were investigated with PAHs.
acidic compounds and basic compounds as solutes.
Acidic compounds were absorbed strongly on the column, parts of them
having irreversible absorption on the stationary phase; basic compounds had
reasonable retention with symmetrical peaks; PAHs were eluted with little
absorption. All above investigations showed that there were Bronsted acid sites
and Lewis acid sites on the surface of alumina.
(iii) Taking advantage of Lewis acid sites on the surface of alumina, we
modified the columm of alumina with a Lewis base of minoethylphosphoric
acid. The chromatographic performance of the modified column was evaluated
under binary eluents and compared with that of the column of alumina.
The results showed that the lewis acid sites on the surface of alumina
were entirely covered with minoethylphosphoric acid. Acidic compounds
could be eluted yet with poorly symmetrical peaks. The retention behaviors of
PAHs have difference from ones on the column of alumina; The seperating
factors of some compunds were also improved greatly.
(iv) We succeed in preparating the column of alumina modified with P-
cyclodextrine, and studied the retention behaviors of aromatic compounds on
the a-CD-modified column. The comparision of the n-CD-modified column with
the aminoacid-modified one confirmed the existence of inclusion equilibrium
between yclodextrine and sample molecules. The capacity factors of the
sample generally incresed by virtue of the specific interaction between j3-
cyclodextrine and sample molecules. The effects of the substituents and their
relative postion on the aromatic rings and the mobile phase were examined,
some enanitiomers were seperated suceessfully.
Key words: Zirconia-alumina,alumina,β-a
很大的互补性，在某些物理化学性质上还具有一定优势。但ZrO_2的孔结构不够
理想，Al_2O_3的改性困难在很大程度上限制了它们在高效液相色谱中作为固定
相的应用。针对这两个问题，本论文进行了如下工作：
（i）用溶胶—凝胶法制备了ZrO_2—Al_2O_3复合氧化物填料，研究了氧化物微
球的孔结构、孔径、孔容、比表面积、表面耐碱性，并用β-氨基乙膦酸对其进行了
改性，系统地研究了改性ZrO_2-Al_2O_3的正相色谱性能。考察了流动相性质和组
成对溶质的保留行为的影响和酸性、碱性、中性化合物在改性ZrO_2—Al_2O_3上的
色谱行为。
芳香族化合物在该固定相的HPLC保留行为表明：采用吸附法对ZrO_2—
Al_2O_3复合氧化物的改性是可行的。该固定相表现出一些氨基键合硅胶固定相
类似的色谱性能：对酚的保留较强，对芳烃的保留较弱；一些芳香胺化合物的容
量因子的对数与极性溶剂在流动相中的比例的对数成良好的线性关系。
（ii）用酸腐蚀法制备了Al_2O_3固定相，以不同的流动相评价了其正相色谱性
能，考察了酸性、碱性、中性化合物在Al_2O_3固定相上的色谱行为。酸性化合物的
保留较强，部分酸性化合物出现不可逆吸附；碱性化合物保留适中，峰形较为对
称，中性化合物保留甚弱。上述的色谱保留行为说明在Al_2O_3表面存在有
Bronsted酸性中心和Lewis酸性中心。
（iii）利用Al_2O_3表面存在的Lewis酸性中心，用Lewis碱β-氨基乙膦酸对
Al_2O_3进行了改性，用二元流动相评价了其色谱性能，并与Al_2O_3固定相的色谱
性能进行了比较。
结果表明：Lewis酸性中心已被β-氨基乙膦酸覆盖，酸性化合物得以洗脱，
但峰形仍旧不好。中性化合物的保留行为与在Al_2O_3固定相上的保留亦有所不
同，部分碱性化合物的分离选择性得到了提高。
（iv）制备了β-环糊精改性Al_2O_3固定相，以苯及萘的衍生物考察了β-环糊
精改性Al_2O_3的色谱性能，并与相同条件下β-氨基乙膦酸改性Al_2O_3的色谱性
卜奎氯J巧士学上论丈
＼‘。、。。、。／．二二二于＜丁、厂二，口
能进行了比较，分析了卜环糊精改性AI0。固定相的保留机制：溶质分子在尺寸
上与卜环糊精的匹配程度、氢键的形成都影响着溶质的保留。部分对映异构体
在卜环糊精改性川o。固定相上得到了较好的分离。
Metal Oxides, especially zirconia and alumina have been found to be
complementary column packing materials of silica for High ?Performance
Liquid Chromatograph,both of them even showing some advantages of physico
hemical properties over silica. However their applicabilities are often limited
by the poor pore structure of zirconia and the difficulty of modifying alumina
surface. The purposes of our studies are to improve the pore structure of
zirconia and to make the modification of alumina easy and effective.
The main researchs and conclusions in this thesis are as follows:
(i)Zirconialurnina particles were prepared by the sol-gel process. Most
physical properties of them such as pore structure, particle size and specific
surface area were studied. The particles were then modified with 13-aminoethyl
phosphoric acid and served as a new stationary phase. whose chromatographic
performance was evaluated by using ethanol ?oyelohexane, chloroform ?
oyclohexane as mobile phase.
The distinctive chromatographic behaviors of some aromatic compouds on
the modified columm of Zr02-A1203 and the columm of Zr02-A1203 indicated
that it was practable for Zr02-A1203 to be modified with f3-
aminoethylphosphoric acid. Basic compounds such as pyridine~ aniline and
derivatives of them had symmetrical peaks, with poorly shaped peaks of
phenols and polyeyclic aromatie hydrocarbons (PAHs) absorbed poorly on the
modified stationary phase. The logk of some derivatives of aniline had a good
linear relationship with the content of eluent in the mobile phase.
(ii) The particles of alumina were prepared by acid erosion. The
chromatographic performance of the column were investigated with PAHs.
acidic compounds and basic compounds as solutes.
Acidic compounds were absorbed strongly on the column, parts of them
having irreversible absorption on the stationary phase; basic compounds had
reasonable retention with symmetrical peaks; PAHs were eluted with little
absorption. All above investigations showed that there were Bronsted acid sites
and Lewis acid sites on the surface of alumina.
(iii) Taking advantage of Lewis acid sites on the surface of alumina, we
modified the columm of alumina with a Lewis base of minoethylphosphoric
acid. The chromatographic performance of the modified column was evaluated
under binary eluents and compared with that of the column of alumina.
The results showed that the lewis acid sites on the surface of alumina
were entirely covered with minoethylphosphoric acid. Acidic compounds
could be eluted yet with poorly symmetrical peaks. The retention behaviors of
PAHs have difference from ones on the column of alumina; The seperating
factors of some compunds were also improved greatly.
(iv) We succeed in preparating the column of alumina modified with P-
cyclodextrine, and studied the retention behaviors of aromatic compounds on
the a-CD-modified column. The comparision of the n-CD-modified column with
the aminoacid-modified one confirmed the existence of inclusion equilibrium
between yclodextrine and sample molecules. The capacity factors of the
sample generally incresed by virtue of the specific interaction between j3-
cyclodextrine and sample molecules. The effects of the substituents and their
relative postion on the aromatic rings and the mobile phase were examined,
some enanitiomers were seperated suceessfully.
Key words: Zirconia-alumina,alumina,β-a
引文
(1)邹汉法、张玉奎、卢佩章，《高效液相色谱法》，科学出版社，1998
(2)P. R. Brown, R. A. Hartwich, High Perfermance Liquid Chromatography. Chapter 4,J. H. Knox, B. Kaur, Wiley-Interscience Publ. Jhon Wiley ＆ sons, 1989
(3)S. Yamamoto, K. Nakanishi, R. Matsuo, Ion Exchange Chromatography of proteins,Marcel Dekker Inc., New York. and Basel,1988.
(4)J. Nawroki, Chromatographia, 1991,31,177
(5)J. Nawroki, Chromatographia, 1991,31,193
(6)J. Nawroki, Chromatographia. A, 1997,779,29
(7)M. Stadalius, LC—GC, 1998,6,494
(8)M. D. Henry,J Chromatogr., 1991,544,413
(9)D. V. Molalley,J. Chromatogr., 1990,506,357
(10)R. F. M. Vervoort,F. A. Maris, H. Himdriks, J. Chromatogr. 1992,623,207
(11)M. J. Wirth, R. W. P. Fairbank, H. O. Fatunmbi, Science, 1997,275,44
(12)左育民，许晓文，分析化学，1998，26(5)，593
(13)M. Hanson, A. Kurganov, K. K. Vnger, V. A. Davankov, J. Chromatogr. A, 1993, 656,369
(14)G. Schomburg,Trends Anal. Chem. 1991,10,163
(15)W. H. Tomb. H.H. Weetall,U. S. Patent,1974,1013783
(16) R. Aigner-Held.W. A. Aue.E. E. Pi ckett.J. Chromatogr. , 1980,189,139
(17) R. W. Stout, J.J. DeStefanoJ.Chrmatogr. , 1985,326,63
(18) W. K. Kreis and K. K. Unger, Adsorption at the Gas Solid and Liquid-Solid Interface, Amsterdam,Elserier,p373,1982
(19) T. Ono,et al. , Preparation of Catalysis 3,Amsterdam,Elsevier,P631,1983
(20) J. B. Peri,J. Phys. Chem. ,1965,69,220．
(21) C. J.C. M.Laurent, H. A. H. Billiet and L. de Galan, Chromatogrophia, 17(1983) 253． (On the use of alumina in HPLC with aqueous mobile phases at extreme pH)
(22) C. J.C. M. Laurent, H. A.M. Billiet and L. de Galan,Chromatogrophia, 17(1983) 394
(23) C. J. C. M. Laurent,H. A. H. Billiet and L. de Galan,J. Chromatogr. ,285(1984) 161-170
(24) C. J. C. M. Laurent, H. A. H. Billiet and L. de Galan,Chromatogrophia, 17 (1983) 394
(25) R.V. Arenas,J. P. Foley,Analyst,1994,119,1303
(26) J. E. Haky.A. Raghari,B. M. Dunn,J. Chromatogr. 1991,541,303
(27) K. B. Holland,J. M. Washingtm, D. C. Moe,C. M. Contoy, Am. Lab. ,1992,24 (3) ,51
(28) K. Cabrera,D. Lubda, G.Jung, Kontakte, 1992,1,32．
(29) J. J. Pesek and H. D. Lin,Chromatographia,28,565(1989)
(30) M. Kawahara,H. Nakamara,T. Nakajima. Anal. Sci. 1988,4,671
(31) M. Kawahara,H. Nakamura,T. Nakamura. Anal. Sci. 1989,4,485
(32) Trudinger U. MaUer G,Unger K. K,J. Chromatogr. 1990,535:11
(33) Kurganov A. A,Trudinger U.Isaeva T,Unger K. K,Chromatographia,1996,42: 217
(34) Blalkwell J. A ,Carr P. W, J. Chromatogr. , 1991,549:59
(35) Clausen A. M.Carr P. W, Anal. chem. ,1998,70:378-385
(36) Nawrocki J. Rigney M. P,McCormick A,Carr P. W,J. Chromatogr. , 1993,657, 229
(37) M. P. Rigney,T. P. Weber and P. W. Carr,J. Chromatogr. ,484(1989) 273．
(38) M. Kawahara ,H. Nakamura ,T. Nakajima. J. Chromatogr. , 1990,515,149．
(39) U.Trudinger,G.Muller ,K.K.Unger,J.Chromatogr. ,1990,535,111
(40) P. W. Carr,E. F. Funkenbusch,M. P. Rigney,P. L. Coleman.D. L. Hanggi.W. A. Schafer,U. S. Patent, 1991,5015373
(41) L. Sun,M. J. Annen,F. Lorenzano-porias, P. W. Carr, A. U. McCormick, J. Colloid Interface Sci. 1994,163,464
(42) C. F. Lorrenzano-Porras,P. W. Carr, A. Mclormick, J. Colloid Interface Sci. , 1994,164． 1
(43) M. J. Annen,R. Kizhappali,P. W. Carr. A. Mccormizk, J. Mater. Sci. ,1994,29, 6123
(44) C. F. Lorenzano-Porras, D. H. Reeder, M. J. Annen, P. W. Carr. A. V. Mccormick,Ind. Eng. chem. Res. ,1995,34,2719
(45) P. D. L. Mercena ,J. G. Van Ommen,E. B. M. Doesbury, A. J. Burggraaf ,J. R. H. Ross,Appl. Catal. , 1990,57． 127
(46) C. F. Lorrenzano-Porras,P. W. Carr. A. V. Mclormick,J. Colloid Interface Sci. , 1994,164． 1
(47) C. L. Dunlap,P. W. Carr. A. V. Mccormick,Chromatographia,1996,42,273
(48) R. A. Shalliker,G. K. Douglas. J. Lig. Chrom. & Rel. Technol, 1997,20(11) , 1651．
(49) Kaneko S,Tsukamoto k,Chem.Lett. 1983:1425
(50) FengY-Q,Zhang Q-H,Da S-L,Zhang Y. Anal. Sci. ,2000,16(6) :in Press.
(51) Zhang Q-H,Feng Y-Q,Da S-L,Anal.Sci. ,1999,15:767-772
(52) Zhang Q-H,Feng Y-Q,Da S-L,Chromatographia 1999,50:654-660
(53) K. K.Unger,U. Trudinyer,Chem. Anal. ,1989,98,145
(54) U. Trudinger,G. mailer,K. K. UngerJ. Chromatogr. ,1990,535,111
(55) M. Grun,A. A Kurganov,S. Schacht,F. Schuth,K. K. Vnger,J. Chromatogr. , 1996,740,1
(56) A. A. Kurganov,U. Trudinger,T. Isaeva,K. K. Uager,Chromatogr. ,1996,740,1
(57) J. A. Blackwell,P. W. Carr,J. Chromatogr. ,1991,549,59
(58) W. A. Schafer, P. W. Carr. E. F. Fankenbusch, K. A. Parsm.J. Chromatogr. , 1991,587,149
(59) M. P.Rigrey,Ph. D. Thesis,University of Minnesota,Minneapolis. MN. 1989．
(60) J. Yu,Z. E. Rassi J. Chromatogr. ,1993,631,91
(61) H. J. Writh.K. O. Eriksson,P. Holt,M. Aguilar.M. T. W. Hearn,J. Chromatogr. , 1993,646,129
(62) H.J. Writh.M.T. W. Hearn,J. Chramatogr, 1993,646,143
(63) H. J. Writh,J. Chromatogr. , A, 1995,711,223
(64) M. P. Righey ,T. P. Weker,P. W. Carr. J. Chromatogr. , 1989,484,273
(65) E. F. Funkenbush ,Eur. Patent, 1991,448302
(66) J. Li,P. W. Carr. Anal.Chem. ,1997,69,2193
(67) L. M. Shargin.V. M. Galkin,V. E. Moissev,et al. Zhur. Fiz. Khim. ,1991,66, 2677
(68) C. Mcneff, Q.H.Zhao, P. W. Carr, J. Chromatagr. A,1994,684,201
(69) C. L. Dunlap,P. W. Carr,J. Chromatogr. ,1996,746,199
(70) M. H. Glavanovich.P. W. Carr. Anal. Chem. 1994,66,2584
(2)P. R. Brown, R. A. Hartwich, High Perfermance Liquid Chromatography. Chapter 4,J. H. Knox, B. Kaur, Wiley-Interscience Publ. Jhon Wiley ＆ sons, 1989
(3)S. Yamamoto, K. Nakanishi, R. Matsuo, Ion Exchange Chromatography of proteins,Marcel Dekker Inc., New York. and Basel,1988.
(4)J. Nawroki, Chromatographia, 1991,31,177
(5)J. Nawroki, Chromatographia, 1991,31,193
(6)J. Nawroki, Chromatographia. A, 1997,779,29
(7)M. Stadalius, LC—GC, 1998,6,494
(8)M. D. Henry,J Chromatogr., 1991,544,413
(9)D. V. Molalley,J. Chromatogr., 1990,506,357
(10)R. F. M. Vervoort,F. A. Maris, H. Himdriks, J. Chromatogr. 1992,623,207
(11)M. J. Wirth, R. W. P. Fairbank, H. O. Fatunmbi, Science, 1997,275,44
(12)左育民，许晓文，分析化学，1998，26(5)，593
(13)M. Hanson, A. Kurganov, K. K. Vnger, V. A. Davankov, J. Chromatogr. A, 1993, 656,369
(14)G. Schomburg,Trends Anal. Chem. 1991,10,163
(15)W. H. Tomb. H.H. Weetall,U. S. Patent,1974,1013783
(16) R. Aigner-Held.W. A. Aue.E. E. Pi ckett.J. Chromatogr. , 1980,189,139
(17) R. W. Stout, J.J. DeStefanoJ.Chrmatogr. , 1985,326,63
(18) W. K. Kreis and K. K. Unger, Adsorption at the Gas Solid and Liquid-Solid Interface, Amsterdam,Elserier,p373,1982
(19) T. Ono,et al. , Preparation of Catalysis 3,Amsterdam,Elsevier,P631,1983
(20) J. B. Peri,J. Phys. Chem. ,1965,69,220．
(21) C. J.C. M.Laurent, H. A. H. Billiet and L. de Galan, Chromatogrophia, 17(1983) 253． (On the use of alumina in HPLC with aqueous mobile phases at extreme pH)
(22) C. J.C. M. Laurent, H. A.M. Billiet and L. de Galan,Chromatogrophia, 17(1983) 394
(23) C. J. C. M. Laurent,H. A. H. Billiet and L. de Galan,J. Chromatogr. ,285(1984) 161-170
(24) C. J. C. M. Laurent, H. A. H. Billiet and L. de Galan,Chromatogrophia, 17 (1983) 394
(25) R.V. Arenas,J. P. Foley,Analyst,1994,119,1303
(26) J. E. Haky.A. Raghari,B. M. Dunn,J. Chromatogr. 1991,541,303
(27) K. B. Holland,J. M. Washingtm, D. C. Moe,C. M. Contoy, Am. Lab. ,1992,24 (3) ,51
(28) K. Cabrera,D. Lubda, G.Jung, Kontakte, 1992,1,32．
(29) J. J. Pesek and H. D. Lin,Chromatographia,28,565(1989)
(30) M. Kawahara,H. Nakamara,T. Nakajima. Anal. Sci. 1988,4,671
(31) M. Kawahara,H. Nakamura,T. Nakamura. Anal. Sci. 1989,4,485
(32) Trudinger U. MaUer G,Unger K. K,J. Chromatogr. 1990,535:11
(33) Kurganov A. A,Trudinger U.Isaeva T,Unger K. K,Chromatographia,1996,42: 217
(34) Blalkwell J. A ,Carr P. W, J. Chromatogr. , 1991,549:59
(35) Clausen A. M.Carr P. W, Anal. chem. ,1998,70:378-385
(36) Nawrocki J. Rigney M. P,McCormick A,Carr P. W,J. Chromatogr. , 1993,657, 229
(37) M. P. Rigney,T. P. Weber and P. W. Carr,J. Chromatogr. ,484(1989) 273．
(38) M. Kawahara ,H. Nakamura ,T. Nakajima. J. Chromatogr. , 1990,515,149．
(39) U.Trudinger,G.Muller ,K.K.Unger,J.Chromatogr. ,1990,535,111
(40) P. W. Carr,E. F. Funkenbusch,M. P. Rigney,P. L. Coleman.D. L. Hanggi.W. A. Schafer,U. S. Patent, 1991,5015373
(41) L. Sun,M. J. Annen,F. Lorenzano-porias, P. W. Carr, A. U. McCormick, J. Colloid Interface Sci. 1994,163,464
(42) C. F. Lorrenzano-Porras,P. W. Carr, A. Mclormick, J. Colloid Interface Sci. , 1994,164． 1
(43) M. J. Annen,R. Kizhappali,P. W. Carr. A. Mccormizk, J. Mater. Sci. ,1994,29, 6123
(44) C. F. Lorenzano-Porras, D. H. Reeder, M. J. Annen, P. W. Carr. A. V. Mccormick,Ind. Eng. chem. Res. ,1995,34,2719
(45) P. D. L. Mercena ,J. G. Van Ommen,E. B. M. Doesbury, A. J. Burggraaf ,J. R. H. Ross,Appl. Catal. , 1990,57． 127
(46) C. F. Lorrenzano-Porras,P. W. Carr. A. V. Mclormick,J. Colloid Interface Sci. , 1994,164． 1
(47) C. L. Dunlap,P. W. Carr. A. V. Mccormick,Chromatographia,1996,42,273
(48) R. A. Shalliker,G. K. Douglas. J. Lig. Chrom. & Rel. Technol, 1997,20(11) , 1651．
(49) Kaneko S,Tsukamoto k,Chem.Lett. 1983:1425
(50) FengY-Q,Zhang Q-H,Da S-L,Zhang Y. Anal. Sci. ,2000,16(6) :in Press.
(51) Zhang Q-H,Feng Y-Q,Da S-L,Anal.Sci. ,1999,15:767-772
(52) Zhang Q-H,Feng Y-Q,Da S-L,Chromatographia 1999,50:654-660
(53) K. K.Unger,U. Trudinyer,Chem. Anal. ,1989,98,145
(54) U. Trudinger,G. mailer,K. K. UngerJ. Chromatogr. ,1990,535,111
(55) M. Grun,A. A Kurganov,S. Schacht,F. Schuth,K. K. Vnger,J. Chromatogr. , 1996,740,1
(56) A. A. Kurganov,U. Trudinger,T. Isaeva,K. K. Uager,Chromatogr. ,1996,740,1
(57) J. A. Blackwell,P. W. Carr,J. Chromatogr. ,1991,549,59
(58) W. A. Schafer, P. W. Carr. E. F. Fankenbusch, K. A. Parsm.J. Chromatogr. , 1991,587,149
(59) M. P.Rigrey,Ph. D. Thesis,University of Minnesota,Minneapolis. MN. 1989．
(60) J. Yu,Z. E. Rassi J. Chromatogr. ,1993,631,91
(61) H. J. Writh.K. O. Eriksson,P. Holt,M. Aguilar.M. T. W. Hearn,J. Chromatogr. , 1993,646,129
(62) H.J. Writh.M.T. W. Hearn,J. Chramatogr, 1993,646,143
(63) H. J. Writh,J. Chromatogr. , A, 1995,711,223
(64) M. P. Righey ,T. P. Weker,P. W. Carr. J. Chromatogr. , 1989,484,273
(65) E. F. Funkenbush ,Eur. Patent, 1991,448302
(66) J. Li,P. W. Carr. Anal.Chem. ,1997,69,2193
(67) L. M. Shargin.V. M. Galkin,V. E. Moissev,et al. Zhur. Fiz. Khim. ,1991,66, 2677
(68) C. Mcneff, Q.H.Zhao, P. W. Carr, J. Chromatagr. A,1994,684,201
(69) C. L. Dunlap,P. W. Carr,J. Chromatogr. ,1996,746,199
(70) M. H. Glavanovich.P. W. Carr. Anal. Chem. 1994,66,2584