WO2001051163A1 - Chromatographic and electrophoretic separation of chemicals using electrically conductive polymers - Google Patents
Chromatographic and electrophoretic separation of chemicals using electrically conductive polymers Download PDFInfo
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- WO2001051163A1 WO2001051163A1 PCT/US2001/000973 US0100973W WO0151163A1 WO 2001051163 A1 WO2001051163 A1 WO 2001051163A1 US 0100973 W US0100973 W US 0100973W WO 0151163 A1 WO0151163 A1 WO 0151163A1
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- poly
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- 238000000926 separation method Methods 0.000 title claims abstract description 49
- 229920001940 conductive polymer Polymers 0.000 title claims abstract description 24
- 239000000126 substance Substances 0.000 title description 24
- 230000005526 G1 to G0 transition Effects 0.000 claims abstract description 33
- 229920000642 polymer Polymers 0.000 claims abstract description 32
- 229920000867 polyelectrolyte Polymers 0.000 claims abstract description 10
- 229920000547 conjugated polymer Polymers 0.000 claims abstract description 9
- -1 plypyrrole Polymers 0.000 claims description 66
- 238000000034 method Methods 0.000 claims description 28
- 229920000767 polyaniline Polymers 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 239000005350 fused silica glass Substances 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 10
- 239000011976 maleic acid Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 7
- 229920002125 Sokalan® Polymers 0.000 claims description 5
- 229920002643 polyglutamic acid Polymers 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 229920002521 macromolecule Polymers 0.000 claims description 4
- 239000011236 particulate material Substances 0.000 claims description 4
- 229920000553 poly(phenylenevinylene) Polymers 0.000 claims description 4
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 claims description 4
- 229920000123 polythiophene Polymers 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims 3
- 239000011343 solid material Substances 0.000 claims 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims 2
- 239000012056 semi-solid material Substances 0.000 claims 1
- 238000006467 substitution reaction Methods 0.000 claims 1
- 238000000576 coating method Methods 0.000 description 32
- 239000011248 coating agent Substances 0.000 description 26
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000001962 electrophoresis Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- 239000002773 nucleotide Substances 0.000 description 12
- 230000005012 migration Effects 0.000 description 11
- 238000013508 migration Methods 0.000 description 11
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 230000003993 interaction Effects 0.000 description 9
- 125000003729 nucleotide group Chemical group 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000005251 capillar electrophoresis Methods 0.000 description 7
- 229940093499 ethyl acetate Drugs 0.000 description 7
- 235000019439 ethyl acetate Nutrition 0.000 description 7
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 7
- 239000004926 polymethyl methacrylate Substances 0.000 description 7
- 235000018102 proteins Nutrition 0.000 description 7
- 102000004169 proteins and genes Human genes 0.000 description 7
- 108090000623 proteins and genes Proteins 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 239000000872 buffer Substances 0.000 description 6
- 238000005370 electroosmosis Methods 0.000 description 6
- 229920000447 polyanionic polymer Polymers 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000008351 acetate buffer Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
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- 102000009027 Albumins Human genes 0.000 description 3
- 108010088751 Albumins Proteins 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
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- 238000005886 esterification reaction Methods 0.000 description 3
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- 239000000178 monomer Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000012491 analyte Substances 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
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- 230000004001 molecular interaction Effects 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 229920000805 Polyaspartic acid Polymers 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 230000000994 depressogenic effect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
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- 239000011521 glass Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000013101 initial test Methods 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
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- 230000000670 limiting effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N methyl acetate Chemical group COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 230000037230 mobility Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
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- 239000006174 pH buffer Substances 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
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- 125000005372 silanol group Chemical group 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
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- 238000000825 ultraviolet detection Methods 0.000 description 1
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- 238000001429 visible spectrum Methods 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
- B01D15/20—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the conditioning of the sorbent material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/401—Polymers based on the polymerisation of acrylic acid, e.g. polyacrylate
- B01D71/4011—Polymethylmethacrylate
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/72—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of the groups B01D71/46 - B01D71/70 and B01D71/701 - B01D71/702
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J20/286—Phases chemically bonded to a substrate, e.g. to silica or to polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
- B01J20/3204—Inorganic carriers, supports or substrates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
- B01J20/3268—Macromolecular compounds
- B01J20/327—Polymers obtained by reactions involving only carbon to carbon unsaturated bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
- B01J20/3268—Macromolecular compounds
- B01J20/3272—Polymers obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
- B01J20/3268—Macromolecular compounds
- B01J20/3276—Copolymers
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/447—Systems using electrophoresis
- G01N27/44704—Details; Accessories
- G01N27/44747—Composition of gel or of carrier mixture
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/447—Systems using electrophoresis
- G01N27/44704—Details; Accessories
- G01N27/44752—Controlling the zeta potential, e.g. by wall coatings
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/50—Conditioning of the sorbent material or stationary liquid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
- B01D15/36—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving ionic interaction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/80—Aspects related to sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J2220/86—Sorbents applied to inner surfaces of columns or capillaries
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
- G01N2030/285—Control of physical parameters of the fluid carrier electrically driven carrier
Definitions
- This invention relates to the synthesis and use of double stranded polymers to separate chemical mixtures.
- a neutral component has a polar character then it will be retained longest by a polar stationary phase.
- Neutral non-polar solutes will be retained best by a non-polar stationary phase.
- the mobile phase can be liquid, a gas or a supercritical fluid.
- the stationary phase can be a packed or wall coated standard or capillary column. The type of mobile phase determines the name of the method, e.g. liquid chromatography, gas chromatography...etc.
- a conductive polymer, namely single strand polyaniline has been coated on a glassy carbon stationary phase to achieve charge controlled chromatography. The coating allowed the number of ion exchange sites in the stationary phase to be controlled instead of being fixed as in ion chromatography and inorganic anions and organic acids were separated.
- a drawback of coating the single strand polyaniline on the stationary phase is that the single strand polyaniline does not have a wide enough pH range to be usable.
- Electrophoresis creates separations of charged molecules. Electrophoresis is principally used for the separation of biological molecules and remains a standard biological tool. Charged molecules can be separated in slab gels by the application of an electric field. Capillary electrophoresis separates charged molecules according to their electrophoretic mobilities in an electric field. Generally, the separation compartment is a narrow fused silica capillary filled with an electrolyte solution. The electric field is applied with an external voltage source between two electrodes in small vials in contact with the electrolyte solution at both ends of the capillary. The sample is introduced either hydrostatically or electro migration as a narrow zone at one end of the capillary. Typically, UV detection takes place at the other end of the capillary.
- Fused silica is the typical capillary material used in capillary electrophoresis because it is inexpensive, easy to fabricate into capillaries with internal diameters in the 10-300 ⁇ m ranges, possesses optical transparency for both UV and visible spectrums, is mechanically strong and is flexible when coated with polyimide.
- the material properties of fused silica presents some drawbacks when used in capillary elecrophoresis.
- the surface silanol groups of the fused silica behave as a weak acid, ionizing in water, with a broad titration curve in the pH 3.9 to 9 region. These surface anionic groups induce both electro osmotic flow (EOF) and solute wall interactions to occur.
- EEF electro osmotic flow
- Solute wall interactions typically occur with cationic proteins that electrostatically bind to the silica. Reversible interactions between such analytes and the capillary surface worsen the separation profile, broadening the peaks and decreasing reproducibility, while irreversible interactions can destroy the flow profile entirely. Attempts to reduce these interactions include the use of extreme pH buffers (very high and very low), the use of additives and modification of the capillary surface.
- the present invention provides a coating for the stationary phase of a chemical separation system, the coating comprising a double stranded conductive polymer that is efficient, effective and overcomes the drawbacks associated with existing chemical separation systems.
- the invention comprises a double stranded conductive polymer functioning as the stationary phase of a chemical and/or biological separation system.
- the double stranded conductive polymer provides controllable interactions between the polymer system of the stationary phase and the chemicals and/or biological analyte in a carrier stream.
- the invention further comprises a chemical separation system comprised of stationary phase comprising a double stranded polymer.
- the double stranded conductive polymer used in the invention comprises a linear strand of polyaniline and a linear strand of a poly electrolyte twisted together to form a macro-molecule.
- the polyaniline strand can be modified to predictably change its hydrophobicity and/or its color when the pH and/or the electrochemical potential within the separation system is changed.
- the modification of the polyaniline strand controls the analyte-surface interactions to improve the separation.
- the linear strand of polyelectrolyte provides the properties suitable for non-aggressive interactions with the analyte or carrier stream.
- the double stranded conductive polymers can be used as a part of the stationary phase in a chromatographic column, as a coating on the inner surface of a capillary for separation by capillary electrophoresis, as part of a filtration membrane, as a component in gel electrophoresis and/or coated on or admixed with particulate material packed in a column or the like.
- the double stranded conductive polymer has the chemical structure that is suitable for selective interaction with molecules dissolved in a carrier fluid that flows by the polymer to effect chemical separation of the components in the mixture.
- the double stranded conductive polymers used for chemical separation belong to a class of polymers comprising a molecular complex of two strands of polymers: (1) a ⁇ - conjugated polymer such as polyaniline, plypyrrole, polythiophen, poly(phenylene vinylene), etc. and (2) a polyelectrolyte such as poly(acrylic acid), poly(methylvinylether-co-maleic acid), poly(butadiene-co-maleic acid), poly(vinylsulfonic acid), poly(styrenesulfonic acid), poly(methacrylic acid), poly(L- glutamic acid), poly(L- Asparic acid), etc.
- a ⁇ - conjugated polymer such as polyaniline, plypyrrole, polythiophen, poly(phenylene vinylene), etc.
- a polyelectrolyte such as poly(acrylic acid), poly(methylvinylether-co-maleic acid), poly(butadiene
- the two strands of the molecular complex are bonded non-covalently for most of the applications, although crosslinking between the two strands is also possible.
- the synthetic process (the template-guided synthesis) allows the control of solubility, conformation, and the morphology of the polymer and thus provides advantageous properties for chemical separation applications.
- the two strands of polymers in the molecular complex are likely to be non-covalently bonded in a side-by-side arrangement thus they are referred to as double-stranded polymers, although the actual structure of the complex could be somewhat random.
- a double stranded conductive polymer was coated on the inner suface of a glass capillary in a capillary electrophoretic separation apparatus.
- the electro osmotic flow (EOF) carried the chemical mixture through the capillary. Due to the influence of the ⁇ - conjugated polymers coated on the capillary wall, the different types of molecules in the mobile phase are separated by their difference in elution time.
- the present invention embodies coatings for improving the analysis of organic and inorganic species by chromatographic and electrophoretic techniques. These experiments demonstrate the beneficial molecular interaction between the stationary and the mobile phases. The same molecular interactions can be used for liquid chromatography, HPLC, of thin-layer chromatography for chemical analysis.
- the double stranded conductive polymers are also useful for large-scale separation of chemicals or drugs when it is used as a component in preparative-scale chromatography or as part of a membrane for selective filtration of chemicals.
- the double stranded polymer used for the preferred embodiment comprises two components: (1) a polyaniline molecule, and (2) a polyanion. These two strands of polymers are bonded by non-covalent intermolecular interactions to form a stable molecular complex.
- Examples of the polyanion in the polymeric complexes are poly(stryrenesulfonic acid), poly(acrylic acid), poly(methacrylic acid), poly(2-acryamido- 2-methyl-l-propenesulfonic acid), and poly(methylacrylate-co-acrylic acid), poly(butadiene-co-maleic acid), poly(glutamic acid), poly(aspartic acid), etc.
- the double stranded conductive polymers are synthesized to be soluble in water, or soluble in organic solvents, or suspended in latex to satisfy the demands of coatings applications.
- Certain functional groups of the double stranded conductive polymer provide strong adhesion to metals and other polymers, an advantageous property for coatings application for the stationary phase in the separation system.
- the double-strand conductive polymers are synthesized by a method that encourages the formation of molecular complexes.
- aniline monomers are absorbed onto a polyanion chain dissolved in solution.
- the resulting adduct, polyanion:(aniline) x has signatures that can be monitored and verified.
- the attached aniline monomers are oxidatively polymerized to form the polymeric complex.
- the adduct of polyanion:(aniline) x may take the shape of a tight coil or extended chains.
- the shape of the adduct controls the mo ⁇ hology of the polymerized product.
- a tight-coiled adduct results in globular polyaniline complex, while an extended chain adduct results in thin fibers of the double-strand complex aggregates (100 nm diameter x 5 micron length).
- the polyanion functions as a template during the chemical synthesis, and the template becomes the second strand of the "double-strand" polyaniline after polymerization.
- the template guided synthesis allows for controlling the morphology (e.g., fibrous or globular) of the complex as well as the conformation (e.g., coiled or extended chain, helical or sheet conformation) of the polymer.
- the polymer has delocalized electrons on the polymer backbone, the van der Waals and electrostatic interaction of the polymer with the mobile phase can be quite different from the conventional materials for stationary phase.
- This feature is advantageous for separation of proteins, DNA, and drugs because the delocalized binding between the polymer and the analytes can be designed to be specific enough to be selective among the molecules that are otherwise difficult to be separated.
- Fig. 1 A depicts electropherograms for iodide anions on an uncoated capillary.
- Fig. IB depicts electropherograms for iodide anions on a coated capillary.
- Fig. 2A depicts electropherograms for bromide anions on an uncoated capillary.
- Fig. 2B depicts electropherograms for bromide anions on a coated capillary.
- Fig. 3A depicts an electropherogram for nucleotides at a pH of 6 on a coated capillary.
- Fig. 3B depicts an electropherogram for nucleotides at a pH of 6 on an uncoated capillary.
- Fig. 4A depicts an electropherogram for nucleotides at a pH of 7 on a coated capillary.
- Fig. 4B depicts an electropherogram for nucleotides at a pH of 7 on an uncoated capillary.
- Fig. 5A depicts an electropherogram of nucleotides (50 Mm acetate buffer, at a pH of4).
- Fig. 5B depicts an electropherogram of nucleotides (20 Mm acetate buffer, at a pH of 4).
- Fig. 6 A depicts an electropherogram of albumin and glyceraldehydes on a coated capillary.
- Fig. 6B depicts an electropherogram of albumin and glyceraldehydes on an uncoated capillary. Description of the Preferred Embodimentfs ⁇ )
- the double stranded conductive polymer system which is applied to or, alternatively, comprises the stationary phase of the chemical separation system, is polyaniline: polymethylmethacrylate.
- polyaniline: polymethylmethacrylate (PANI: PMMA) disclosed herein is disclosed in International Application No. PCT US96/11646, entitled “Electroactive Polymer Coatings for Corrosion Control” and the same is incorporated by reference in its entirety into this disclosure.
- Step I The mole ratio between the carboxylic acid groups and the aniline monomer units ranged from 2:1 to 1 :1.
- the resulting polymeric complex was soluble or dispersable in water, methanol and ethanol.
- the procedure for synthesis of polyaniline:poly(acrylic acid) complex has been reported supra and the reported procedures were followed.
- the polyaniline :poly (aery lie acid) complex prepared in step 1 was dissolved in methanol. To this solution is added catalytic amount of benzene suflonic acid or toluene sulfonic acid to serve as a catalyst for esterification reaction. The solution was refluxed for 3 days. The esterification reaction converted some of the carboxylic acid group into the methyl acetate group. This lowered the solubility of the complex in methanol and the polymeric complex precipitated out of the solution. The precipitate was filtered out and dissolved in ethyl acetate.
- the precipitate could be redissolved in 1 : 1 mixture of ethylacetate and methanol, and the solution further refluxed until precipitate was again formed.
- This precipitate was soluble in pure ethyl acetate but is not soluble 1:1 mixture of ethyl acetate and methanol.
- a dilute solution of the polymer in ethyl acetate was pushed through a fused silica capillary.
- the capillary (s) used were polyimide coated fused silica 100 to 300 mm inner diameter).
- a small amount of the polymer was sealed in a vial and the end of the capillary pushed through the seal. An air filled syringe was also pushed through the seal.
- the concentration of the polymeric solution was determined to be approximately 2.1 g/L.
- the solution was diluted in ethyl acetate to produce a solution that was 0.1% in ethyl acetate.
- the capillary was pretreated
- the coating was present on the capillary surface as illustrated by the differences obtained on the uncoated and coated capillaries.
- An increase in pH was accompanied by an increase in migration time for the bare capillary and a decrease in migration for the coated capillary.
- the coating affects the elution of anions in the capillary and the coating was changing with the pH of the solution.
- Example II Monophosphate Nucleotides
- PANI PMMA as a coating for a capillary in capillary electrophoresis is present and effective for the analysis of small, biological molecules.
- the following results reveal the effect of pH and buffer concentration on the coated capillary and the effectiveness of pre-treating the fused silica capillary as part of the coating procedure.
- the capillaries were coated using procedure 2.
- the separation conditions were +20kV, a 20Mm acetate buffer, an injection time of 10s and the separation was performed on a Waters Quanta capillary electrophoreses system.
- the capillaries were coating using procedure 1.
- the separation conditions were +20kV, a 50Mm phosphate buffer, an injection time of 10s and the separation was performed on a Waters Quanta capillary electrophoresis system.
- the migration order differences of the nucleotides in the coated and uncoated capillaries revealed the presence of the coating and the difference in behavior between the coating and fused silica. It can be seen that there is a large difference in migration times for the capillaries at a pH of 7 and that the coated capillary presents a large advantage at this pH. The two capillaries were the same size and the difference cannot be attributed to any feature other than the presence of the coating. Additional experiments were performed to reveal the what effect the coated capillaries had at different concentrations of the same buffer differences in the migration times of the monophosphate nucleotides are noted. The initial analysis was all performed with a high concentration buffer (50mM) but later analysis was also performed at 20Mm.
- the coating can be seen to respond to the difference in buffer concentration. The response was highly reproducible. It can be observed that the lower concentration of buffer gives the faster analysis. It can be concluded that at low pH the coating appears to produce excellent separations of nucleotides. It enhances the separations attained by the uncoated capillaries considerably.
- Example II illustrate the ability of the coating to separate, small, biological molecules in a fast, efficient and reproducible manner.
- the following example illustrates the ability of the coating to separate, large, biological molecules, such as proteins, in a fast, efficient and reproducible manner.
- a mixture of albumin and glyceraldehydes was prepared and analyzed.
- the analysis was performed with a 20 Mm borate buffer at a pH of 8, injection time of 20 seconds and an applied voltage of +15kV.
- Coating capillary increased efficiency by one order of magnitude.
- the protein appears to have not eluted and is most likely adhered to the wall of the capillary.
- the protein is seen to elute with good peak shape and in a relatively short amount of time.
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EP01942321A EP1250181A4 (en) | 2000-01-12 | 2001-01-11 | Chromatographic and electrophoretic separation of chemicals using electrically conductive polymers |
AU2001229387A AU2001229387A1 (en) | 2000-01-12 | 2001-01-11 | Chromatographic and electrophoretic separation of chemicals using electrically conductive polymers |
US10/191,683 US6821417B2 (en) | 2000-01-12 | 2002-07-09 | Chromatographic and electrophoretic separation of chemicals using electrically conductive polymers |
US10/859,379 US20040217060A1 (en) | 2000-01-12 | 2004-06-02 | Chromatographic and electrophoretic separation of chemicals using electrically conductive polymers |
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US17570000P | 2000-01-12 | 2000-01-12 | |
US60/175,700 | 2000-01-12 |
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US10/191,683 Continuation US6821417B2 (en) | 2000-01-12 | 2002-07-09 | Chromatographic and electrophoretic separation of chemicals using electrically conductive polymers |
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EP (1) | EP1250181A4 (en) |
AU (1) | AU2001229387A1 (en) |
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CN115572372A (en) * | 2022-10-12 | 2023-01-06 | 潍坊医学院 | Pi-conjugated donor-acceptor-based polymer material with similar structure as well as preparation method and application thereof |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US5547581A (en) * | 1990-04-23 | 1996-08-20 | Andelman; Marc D. | Method of separating ionic fluids with a flow through capacitor |
US6150032A (en) * | 1995-07-13 | 2000-11-21 | The Board Of Governors For Higher Education, State Of Rhode Island And Providence Plantations | Electroactive polymer coatings for corrosion control |
Family Cites Families (3)
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WO1989007265A1 (en) * | 1988-02-03 | 1989-08-10 | Wollongong Uniadvice Limited | Chromatography using electrically conductive polymer stationary phase materials |
US5225495A (en) * | 1991-07-10 | 1993-07-06 | Richard C. Stewart, II | Conductive polymer film formation using initiator pretreatment |
WO1994000215A1 (en) * | 1992-06-22 | 1994-01-06 | Iowa State University Research Foundation, Inc. | Ion chromatographic separations using step and linear voltage waveforms at a charge-controllable polymeric stationary phase |
-
2001
- 2001-01-11 AU AU2001229387A patent/AU2001229387A1/en not_active Abandoned
- 2001-01-11 WO PCT/US2001/000973 patent/WO2001051163A1/en not_active Application Discontinuation
- 2001-01-11 EP EP01942321A patent/EP1250181A4/en not_active Withdrawn
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5547581A (en) * | 1990-04-23 | 1996-08-20 | Andelman; Marc D. | Method of separating ionic fluids with a flow through capacitor |
US6150032A (en) * | 1995-07-13 | 2000-11-21 | The Board Of Governors For Higher Education, State Of Rhode Island And Providence Plantations | Electroactive polymer coatings for corrosion control |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115572372A (en) * | 2022-10-12 | 2023-01-06 | 潍坊医学院 | Pi-conjugated donor-acceptor-based polymer material with similar structure as well as preparation method and application thereof |
CN115572372B (en) * | 2022-10-12 | 2024-05-07 | 潍坊医学院 | Pi-conjugated donor-acceptor-based polymer material with similar structure, and preparation method and application thereof |
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EP1250181A4 (en) | 2003-05-07 |
EP1250181A1 (en) | 2002-10-23 |
AU2001229387A1 (en) | 2001-07-24 |
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