EP0267282A1 - Chromatographic apparatus and process - Google Patents
Chromatographic apparatus and processInfo
- Publication number
- EP0267282A1 EP0267282A1 EP87906042A EP87906042A EP0267282A1 EP 0267282 A1 EP0267282 A1 EP 0267282A1 EP 87906042 A EP87906042 A EP 87906042A EP 87906042 A EP87906042 A EP 87906042A EP 0267282 A1 EP0267282 A1 EP 0267282A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- support material
- organotitanate
- titanium
- alkyl
- alkoxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- 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
- B01J20/287—Non-polar phases; Reversed phases
-
- 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
- B01D15/32—Bonded phase chromatography
- B01D15/325—Reversed phase
-
- 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
- B01D15/361—Ion-exchange
-
- 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
- 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
- B01J20/3202—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
-
- 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
- B01J20/3202—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
- B01J20/3206—Organic carriers, supports or substrates
- B01J20/3208—Polymeric carriers, supports or substrates
- B01J20/3212—Polymeric carriers, supports or substrates consisting of a polymer obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
-
- 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
- B01J20/3214—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the method for obtaining this coating or impregnating
- B01J20/3217—Resulting in a chemical bond between the coating or impregnating layer and the carrier, support or substrate, e.g. a covalent bond
- B01J20/3219—Resulting in a chemical bond between the coating or impregnating layer and the carrier, support or substrate, e.g. a covalent bond involving a particular spacer or linking group, e.g. for attaching an active group
-
- 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
- B01J20/3244—Non-macromolecular compounds
- B01J20/3265—Non-macromolecular compounds with an organic functional group containing a metal, e.g. a metal affinity ligand
-
- 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
- B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
- B01J2220/52—Sorbents specially adapted for preparative chromatography
-
- 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
- B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
- B01J2220/58—Use in a single column
-
- 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
- G01N30/60—Construction of the column
- G01N30/6091—Cartridges
Definitions
- This invention relates to separation technology particularly technology for accomplishing chemical separations including separations of biological materials. More particularly, this invention discloses organo-titanate coupled substrates for forming enhanced chromatographic columns or cartridges, including thin layer chromatography (tlc) plates and discloses a process for using coupled substrates for reverse phase and ionic batch separations.
- organo-titanate coupled substrates for forming enhanced chromatographic columns or cartridges, including thin layer chromatography (tlc) plates and discloses a process for using coupled substrates for reverse phase and ionic batch separations.
- silanized support materials especially silanized siliceous support materials in chromatography is well established.
- Various hydroxy bearing inorganic materials are known as support materials including silicates, metal oxides including titanium oxides, clay, bentonite, and glass.
- Chromatographic separation can be based on the difference in rate of migration of different components through a column. Separation is effected by partition of the components between the stationary phase and the mobile phase. Because of the different affinity of components towards the stationary phase, they are eluted at different rates. In reverse phase chromatography the stationary phase is made nonpolar or hydrophobic. The strongest sorption occurs from polar eluents. Reversed phases are most often prepared by reacting silica gel with chloroalkylsilanes or alkoxysilanes. Ion exchange chromatography involves an insoluble matrix having covalently bonded dissociable functional groups at accessible sites.
- the functional groups typically are sulfonic or carboxyl for cation exchanges and tertiary amino or quarternary ammonium groups for anion exchanges. Separation is based on the affinity differences of ions toward their counter-ions in the ion exchange matrix and those dissolved in the eluent.
- Silica gel is the most frequently used adsorbent as it can be prepared in high purity and with various physical properties including specific surface area, pore volume, and pore size. It is inexpensive and its rigidity makes it useful in column chromatography and thin layer chromatographic plates.
- chemically bonding compounds to the silica gel chemically modified chromatographic packing materials have been devised. Typically this involves bonding organic compounds, particularly chloro or alkoxysilanes forming new Si-O-Si bonds. Di- or tri- halo silanes or the corresponding alkoxysilanes are typically employed. Chemically modified silica gel columns possess advantages over conventional particles coated with liquid phase.
- silanizing agents are known for forming chemically modified packing materials, yet these silanes typically involve considerable expense.
- An alternative material, particularly a more cost-effective alternative to silylating agents would be an advance in the art.
- Chemical modifiers for packing materials, until this invention, were almost exclusively restricted to silanes.
- Titanium dioxide has long been recognized as a support material for chromatographic applications.
- Fig. 1 is a view of a chromatographic column.
- Pig. 2 is a view of a chromatographic column wherein the packing material is in an insertable cartridge.
- Fig.3 is an explode view of the chromatographic column and cartridge of Fig. 2.
- Fig. 4 is an alternate design for a chromatographic column also using an insertable cartridge.
- Figs. 5, 6, and 7 are graphical printouts of chromatographic separations of mixtures using organotitanate-treated chromatographic media of the invention. Summary of the Invention
- This invention discloses a new class of chromatographic columns and thin layer chromatography plates based on organotitanate coupled hydroxy bearing solid supports or packing materials useful in reverse phase or ion exchange chromatography.
- the invention discloses essentially a new process for reverse phase or ion exchange chromatographic separations of chemicals by means of organotitanate coupled solid support materials in complete or partial replacement of silanized, chemically modified solid support materials.
- chemicals is understood to include organic chemicals and also biological chemicals such as enzymes, coenzymes, prostoglandins, steroids, lipids, amino acids, and other such chemicals involved in or derived from life processes, all by way of illustration and not limitation.
- the invention discloses a new chromatographic column for reverse phase or ionic chromatographic separation of chemicals from a mixture
- a cartridge having an internal chamber and having entrance and exit orifices, a solid support material within said chamber consisting of a porous hydroxy bearing material, an organotitanate having hydrophobic functionality or an ionizable moiety and chemically coupled to said solid support material by a condensation reaction with the hydroxy groups, coupling means at said entrance and exit orifices for installing the cartridge in the flow path of a fluid mixture.
- the solid support material absent the cartridge can be fashioned into a new thin layer chromatography plate.
- the invention also discloses an improved process for separating chemical substances based on their hydrophobic or ionizable moieties. Separations accomplished by ion exchange or reverse phase chromatography of the type using a stationary phase consisting of a chemically modified support material capable of reversibly fixing macromolecules wherein the improvement comprises: providing a hydroxy bearing support material, reacting the support material with an organotitanate that is a hexavalent coordinate compound or an organotitanate of the formula,
- Ti is tetravalent, wherein R n is a hydrolyzable group linked to titanium through oxygen and is selected from the group consisting of alkoxy.
- n is defined as 2 for purposes of this application when R n is a cyclical group
- R' is a hydrophobic organofunctional group and is selected from the group consisting of alkoxy, aryloxy, alkylester, aerylate, methacrylate, amino aromatic sulfonyl, alkyl aromatic sulfonyl, pyrophosphate, and alkyl phosphato, then contacting the organotitanate reacted support material with a solution mixture of chemical substances one constituent of which has ionizable or hydrophobic functionality so as to reversibly fix the chemical substance to the organotitanate reacted support material, and eluting the fixed chemical substance with an ion containing solution or hydrophobic solvent.
- Figs. 1, 2, 3 and 4 show several designs for chromatographic columns according to this invention wherein the packing material is a hydroxy bearing material coupled by a condensation reaction with an organotitanate to yield a new class of chromatographic columns or cartridges useful for reverse phase or ionic separations.
- Chromatographic columns typically are constructed of a tube or cartridge 1 filled with packing material and attached, connected or coupled to an apparatus, process vessel, or most often an instrument by means of various fittings or coupling means 4.
- the trendin the art is away from fixed cartridges and to the use of replaceable cartridges insertable into a holder to form the column.
- the replaceable cartridge is typically a tube having solid substrate or sorbent within it.
- the cartridge conventionally is fitted with an end cap 4A and bed support.
- the cartridge fits inside the holder tube 2 which has end fittings that compress the caps on the cartridge forming a leak proof seal. Connections to the fluid flow path of an instrument, production apparatus or other vessel, are made directly to the holder tube. Replacing of packing materials in chromatographic columns is simplified by the insertable cartridge concept.
- chromatographic cartridge is intended to encompass both columns that are fixed tubes loaded with organotitanate coupled packing material as in Fig. 1 and also designs using the newer replaceable cartridges or other minor variations.
- chromatograph column is depicted as a fixed cartridge 1 into which is packed organotitanate coupled silica or the hydroxy bearing material.
- Fig. 3 is an exploded view of a typical column using the cartridge concept as in Fig. 2.
- Organotitanate coupled silica or other hydroxy bearing filler can be compressed into cartridge 1 which then fits into holder 2.
- Indicated also is prefilter 6, fittings or coupling means 4 and retaining or compressing rings 5.
- Fig. 4 depicts another chromatographic column also using an insertable cartridge 1 wherein holder 2 is a two part assembly, compressed and held together or released by either depressing or lifting of lever 3.
- This invention discloses a novel class of chromatographic columns based on titanium coupled chromatograhic media.
- the chromatographic material of this invention is a hydroxy bearing substrate material coupled with an organotitanate coupling agent by means of reaction with the surface hydroxyl groups yielding a hydrophobic or ion exchange substrate.
- the organofunctional group can be selected to be useful in reverse phase or ionic chromatography by appropriate selection of functional groups.
- the titanium coupling agent coupled to the solid support material can be characterized by the formula
- titanium coupling agent is of the formula R Ti R'3, wherein R and R' are as above defined.
- the hydrolyzable groups usually are alkoxy. If more than one alkoxy group is a substituent it is evident they need not be the same though such is preferred.
- R is a hydrolyzable group linked to titanium through an oxygen and can be selected for example from the group consisting of alkoxy,
- R is isopropoxy
- R' is organofunctional group having a hydrophobic or ionizable moiety and is linked to titanium through an oxygen.
- R' is selected based on the desired character of the final chromatographic media whether for reverse phase application or ion exchange.
- R' can be dioctylphosphato, tri (dioctylphosphato), or isostearoyl for reverse phase chromatography.
- R' can be an alkyl- or aryl-amino group for anion exchange.
- R' can be a carbonphosphate group for cation exchange or for hydrophobic i.e., reverse phase interactions.
- the hydroxy bearing inorganic or organic substrate materials i.e., X-OH can include various silicas, glass, sand, clay, fiberglass, silica gel, or celluloses or carbohydrates such as dextrans, agarose, or metal oxides. Selection of the substrate is based on the abundance of hydroxy groups.
- the resulting coupled materials have been found useful in chromatographic techniques specifically ion exchange chromatography and reversed phase chromatography thus enabling the construction of new types of chromatographic columns and cartridges. The suitability for particular chromatographic techniques would be dependent on the nature of the organofunctional group attached to titanium, for example, (wherein x is a substrate such as silica):
- Useful titanate coupling agents for forming chromatographic media include monoalkoxy titanate coupling agents such as:
- a B ethylene chelate titanate coupling agents such as:
- di(dioctylphosphato) ethylene titanate 4-aminobenzenesulfonyl dodecylbenzenesulfonyl ethylene titanate
- Coordinate titanate coupling agents such as the following are also useful for forming chemically modified chromatographic substrates:
- the organotitanate coupled chromatographic media of the present invention offers many advantages over conventional chemically modified packing materials.
- the organotitate coupling agents often can be coupled in a single step and without generation of HCI gas as is involved in use of chlorinated silanes. Coupling to the hydroxy bearing surface is typically accomplished by the simple step of coating the surface with the organotitanate.
- the organotitanate can be dissolved in a solvent prior to contacting to the hydroxy bearing surface to effect coupling. Coupling can be enhanced through mild heating, though simple immersion of the hydroxy bearing substrate in the organotitanate at ambient temperature was found suitable to effect coupling in most cases. It may be advantageous with some substrates to expose them to humid conditions prior to coupling to insure a maximum number of possible hydroxy groups available for coupling.
- the organotitanate coupled substrate materials for use in forming novel columns, tlc plates and related chromatographic batch separations can be prepared by coating or contacting the hydroxy bearing substrate material with one of the enumerated organotitanates.
- a dilute organotitanate solution in a solvent such as toluene or other solvent such as isopropanol is employed. While covalent coupling to the hydroxy-bearing surface often can occur at room temperature, it was found advantageous to immerse the substrate in the organotitanate solution and heat to boiling for about 0.5 minute.
- the recovered treated substrate material can then be packed into a column or cartridge or applied to tlc plates. Forming the tlc plate is however best accomplished by immersing the entire tlc plate in the organotitanate solution to treat the finished plate.
- organotitanates typically can be made less expensively than the silane counterparts they can replace, this invention makes large volume batch processes viable.
- the invention encompasses not only new chromatographic columns but also a new process of reverse phase or ion exchange chromatography based on organotitanate coupled solid support materials.
- the stationary phase or support material coupled with organotitanate rather than being placed in a chromatographic column, can be directly added to a reactor vessel.
- a typical process for example a batch process, reverse phase or ionic separation can be accomplished en masse.
- economics attendant to use of silane couplers made batch processing prohibitively expensive.
- the invention discloses an economical and an improved process for separating chemical substances from a solution mixture by reverse phase or ion exchange chromatography of the type using a stationary phase consisting of a chemically modified support material capable of fixing reversibly macromolecules wherein the improvement comprises providing a hydroxy bearing support material such as silica, glass, metal oxide or cellulose preferably as a powder or particulate, then reacting the hydroxy bearing solid support material with any one of the organotitanates specified earlier herein.
- the organotitanate coupled support material is contacted with a solution mixture of chemical substances, one constituent of which has hydrophobic or ionizable functionality, so as to cause reversible fixing of the target chemical substance to the organotitanate reacted support material.
- the target chemical is then recovered with the solid support material.
- the fixed target chemical can be isolated from the other fluids in the reactor vessel.
- the target chemical can be recovered by elution or washing with an ionic solution such as NaCl in ionic exchange or with a hydrophobic solvent for reverse phase separations.
- Titanate treated silica gel as anion exchanger 1. Titanate treated silica gel as anion exchanger.
- Neoalkoxy tri(N-ethylamino-ethylamino) titanate was dissolved in isopropanol to yield a 1% solution (1 g in 100 ml).
- silica gel Amicon, particle size 20-45 urn 250A pore
- 30 ml of the titanate solution was added. The suspension was heated to boiling for 5 minutes, cooled and filtered through a fritted-disc funnel and washed with isopropanol.
- the treated silica gel was packed into a Bio
- the treated silica gel particle size 20-45 urn of the previous example was formed into a slurry in 10 mM potassium phosphate pH 6.8 and packed into a 4.6 mm x 25 cm stainless steel column.
- silica gel thin layer chromatography plates were dipped in 2% isopropyl triisostearoyl titanate in toluene for 5 minutes and air dried. The plates were then washed for 5 minutes in toluene to remove any unreacted isopropyl triisostearoyl titanate.
- the treated silica gel was referred to as "T-SIL”.
- Felt tip pen inks were spotted on each plate and the inks were separated using mixture of acetonitrile and water as a developing solvent.
- Table 1 shows the separation of some inks on T-SIL TLC plates as compared to commercial normal phase and reverse phase TLC plates.
- Red ink and green ink for felt tip pens contain polar components, which did not migrate on normal phase silica gel in a solvent system containing chloroform/methanol (9:1).
- the red ink and green ink components were each separated into two components respectively, using a solvent system containing acetonitrile/- water (5:5).
- the separation of dye components on the isopropyl triisostearoyl titanate treated silica gel plate was similar to that on commercial reverse phase TLC plates, except that the solvent system used was acetonitrile/water (2:8), with much lower consumption of the more expensive organic solvent component.
- the experiment clearly demonstrates the change of normal phase behavior to reverse phase behavior after the silica gel plate was modified by isopropyl triisostearoyl titanate. It also shows that the modified silica gel can be run in a solvent system with high water content to achieve the same separation results. By so doing, the user saves on lower consumption of expensive organic solvent.
- Isopropyl tri(N-aminoethyl-aminoethyl) titanate was an organotitanate bearing both primary and secondary amines, coupled to silica gel and demonstrated as an anion exchanger.
- Silica gel (20-45 urn, 250 A) was reacted with 1% solution (organotitanate/silica gel) of isopropyl tri-(N-aminoethyl-aminoethyl) titanate in isopropanol for 1 hr. The excess organotitanate was removed by washing with isopropanol.
- the modified silica gel was packed into a column, 1 cm x 4.5 cm.
- Protein separation was accomplished with this column by eluting with sodium phosphate buffer at 10 mM, pH 6.8, at a flow rate of 1 ml/min. Protein eluates were monitored spectrophotmetrically at 280 nm. One ml of undiluted rabbit serum sample was separated into two major bands. SDS gel electrophoresis showed that the second contained serum albumin at greater than 90% purity.
- Silica gel (20-45 um, 250 A) was modified by refluxing with 1% isopropyl triisostearoyl titanate in toluene for 1 hour. The excess organotitanate was removed by washing with toluene.
- An aqueous solution of 2,4,5-trichlorophenoxyacetic acid (2,4,5-T, in the free acid form) was prepared by dissolving 0.8 mg of the compound in 5 ml water.
- the aqueous solution of 2,4,5-T was mixed vigorously with the modified silica gel for 2 minutes. Then the solid was separated from the solution by centrifugation. Unadsorbed 2,4,5-T was assayed by absorbance at 286 nm. A decrease in absorbance at 286 nm indicates decreased concentration of 2,4,5-T in the solution.
- the decrease in concentration of 2,4,5-T in the treated solution was proportional to the amount of modified silica gel added ranging from 50 to 400 mg.
- silica gel Fifty grams of silica gel (20-45 urn or 10 urn, 250 A) was heated in 200 ml of 0.1M HCl at 90 C in a sealed bottle for at least 24 hr to maximize the exposure of silanol groups.
- the silica gel was filtered through fritted disc funnel and washed till neutral.
- the acid--treated silica gel was then dried at 150 C for at least 8-12 hours to remove traces of water.
- the dry silica gel was refluxed with 2% isopropyl triisostearoyl titanate in dry toluene for 18 hours.
- the treated silica gel was washed with toluene and dried.
- the silica gel was further reacted with a 2% chlorotrimethylsilane in toluene for 30 minutes. The material was then washed with toluene and dried. The treated silica gel was slurried in acetonitrile and packed into a column 4.6 mm x 25 cm using an Altex pump with a reservoir packer. p-Nitrobenzaldehyde, m-nitroacetanilide, p--nitroanisole were used as model compounds to evaluate the performance of a column packed with 10 um isopropyl tri-sostearoyl titanate modified silica gel (T-SIL).
- T-SIL isopropyl tri-sostearoyl titanate modified silica gel
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Un nouveau type de colonnes chromatographiques pour effectuer une chromatographie à échange d'ions et à phase inverse basée sur un couplage d'organotitanate, ainsi que des procédés de séparation utilisant de tels milieux sont décrits. Les matrices couplées par l'organotitanate utiles pour les séparations chromatographiques ioniques ou à inversion de phase peuvent être constituées en utilisant des agents de couplage de titanate qui remplacent complètement les agents de silanation conventionnels.A new type of chromatographic columns for performing ion phase and reverse phase chromatography based on organotitanate coupling, as well as separation methods using such media are described. Organotitanate-coupled matrices useful for ionic or phase inversion chromatographic separations can be constructed using titanate coupling agents which completely replace conventional silanating agents.
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US85554486A | 1986-04-23 | 1986-04-23 | |
US855544 | 1986-04-23 |
Publications (1)
Publication Number | Publication Date |
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EP0267282A1 true EP0267282A1 (en) | 1988-05-18 |
Family
ID=25321529
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP87906042A Withdrawn EP0267282A1 (en) | 1986-04-23 | 1987-04-22 | Chromatographic apparatus and process |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0267282A1 (en) |
JP (1) | JPH01500147A (en) |
AU (1) | AU7395887A (en) |
WO (1) | WO1987006492A1 (en) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5935866A (en) * | 1989-12-22 | 1999-08-10 | Binax Nh, Inc. | Preparation of sub 100 A magnetic particles and magnetic molecular switches |
US5225282A (en) * | 1991-12-13 | 1993-07-06 | Molecular Bioquest, Inc. | Biodegradable magnetic microcluster comprising non-magnetic metal or metal oxide particles coated with a functionalized polymer |
US5728463A (en) * | 1992-08-07 | 1998-03-17 | Kanto Kagaku Kabushiki Kaisha | Stationary phase material for chromatography |
WO1994003801A1 (en) * | 1992-08-07 | 1994-02-17 | Kanto Kagaku Kabushiki Kaisha | Material of chromatographic stationary phase |
GB9423833D0 (en) * | 1994-11-25 | 1995-01-11 | Euroflow Uk Ltd | Conversion of normal phase silica to reverse phase silica |
CN104194733B (en) * | 2009-03-02 | 2018-04-27 | 霍尼韦尔国际公司 | Thermal interfacial material and manufacture and use its method |
CN109072051B (en) | 2016-03-08 | 2023-12-26 | 霍尼韦尔国际公司 | Phase change material |
US11041103B2 (en) | 2017-09-08 | 2021-06-22 | Honeywell International Inc. | Silicone-free thermal gel |
US11072706B2 (en) | 2018-02-15 | 2021-07-27 | Honeywell International Inc. | Gel-type thermal interface material |
US11373921B2 (en) | 2019-04-23 | 2022-06-28 | Honeywell International Inc. | Gel-type thermal interface material with low pre-curing viscosity and elastic properties post-curing |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4451363A (en) * | 1982-03-03 | 1984-05-29 | Brownlee Labs Inc. | Cartridge for liquid chromatograph |
US4520122A (en) * | 1983-12-05 | 1985-05-28 | Uop Inc. | Immobilization of organic species on refractory inorganic oxides |
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1987
- 1987-04-22 AU AU73958/87A patent/AU7395887A/en not_active Abandoned
- 1987-04-22 EP EP87906042A patent/EP0267282A1/en not_active Withdrawn
- 1987-04-22 WO PCT/US1987/000896 patent/WO1987006492A1/en not_active Application Discontinuation
- 1987-04-22 JP JP62504135A patent/JPH01500147A/en active Pending
Non-Patent Citations (1)
Title |
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See references of WO8706492A1 * |
Also Published As
Publication number | Publication date |
---|---|
JPH01500147A (en) | 1989-01-19 |
AU7395887A (en) | 1987-11-24 |
WO1987006492A1 (en) | 1987-11-05 |
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