WO2002072225A1 - Colonne de chromatographie sol-gel a grande efficacite - Google Patents

Colonne de chromatographie sol-gel a grande efficacite Download PDF

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Publication number
WO2002072225A1
WO2002072225A1 PCT/US2002/007163 US0207163W WO02072225A1 WO 2002072225 A1 WO2002072225 A1 WO 2002072225A1 US 0207163 W US0207163 W US 0207163W WO 02072225 A1 WO02072225 A1 WO 02072225A1
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sol
gel
moieties
derivatives
group
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PCT/US2002/007163
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English (en)
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Abdul Malik
Abuzar Kabir
Chetan Shende
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University Of South Florida
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Priority to US10/471,388 priority Critical patent/US20040129141A1/en
Publication of WO2002072225A1 publication Critical patent/WO2002072225A1/fr
Priority to US11/599,497 priority patent/US8685240B2/en

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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
    • B01J20/291—Gel sorbents
    • 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
    • B01D15/206—Packing or coating
    • 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
    • B01J20/3231—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
    • 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
    • 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
    • G01N30/56—Packing methods or coating methods
    • 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
    • B01J2220/54—Sorbents specially adapted for analytical or investigative 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
    • B01J2220/80—Aspects related to sorbents specially adapted for preparative, analytical or investigative chromatography
    • B01J2220/84—Capillaries
    • 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
    • G01N30/50—Conditioning of the sorbent material or stationary liquid
    • G01N30/56—Packing methods or coating methods
    • G01N2030/567—Packing methods or coating methods coating

Definitions

  • the present invention relates to analytical separation technology and more specifically towards gas chromatography separation systems based on sol-gel stationary phases having improved performance characteristics.
  • GC gas chromatography
  • Capillary GC is a separation technique in which the vapor phase of a sample in a gaseous, mobile phase passes through a capillary tube whose inner walls contain a thin film of an adsorbing or absorbing medium (i.e., stationary phase). Because of differential interactions of the sample components with the stationary phase, the individual components of the sample move through the column with different velocities. This leads to the physical separation of the sample components into individual chromatographic zones as they move down the column with their characteristic velocities. The separated components are detected instrumentally as they are eluted from the column. Contemporary technology for the preparation of open tubular columns is time-consuming.
  • deactivation is usually carried out as a separate step, and involves chemical derivatization of the surface silanol groups.
  • Various reagents have been used to chemically deactivate the surface silanol groups (de Nijs; R.C.M., et al.; Schomburg, G. et al.; Blomberg, L. et al.; and Lee, M.L. et al.). Effectiveness of these deactivation procedures greatly depends on the chemical structure and composition of the fused silica surface to which they are applied.
  • the concentration and mode of distribution of surface silanol groups are of special importance. Because the fused silica capillary drawing process involves the use of high temperatures ( ⁇ 2,000° C), the silanol group concentration on the drawn capillary surface can initially be low due to the formation of siloxane bridges under high-temperature drawing conditions. During subsequent storage and handling, some of these siloxane bridges can undergo hydrolysis due to reaction with environmental moisture. Thus, depending on the post-drawing history, even the same batch of fused silica capillary can have different concentrations of the silanol groups that can also vary by the modes of their distribution on the surface.
  • a typical 30-m long column can require as much as ten hours or more for static coating.
  • the duration of this step can vary depending on the length and diameter of the capillary, and the volatility of the solvent used.
  • the fused silica capillary is filled with a stationary phase solution prepared in a low-boiling solvent.
  • One end of the capillary is sealed using a high viscosity grease or by some other means (Abe, I. et al.), and the other end is connected to a vacuum pump. Under these conditions, the solvent begins to evaporate from the capillary end connected to the vacuum pump, leaving behind the stationary phase that becomes deposited on the capillary inner walls as a thin film.
  • Stationary phase film of desired thickness could be obtained by using a coating solution of appropriate concentration that can be easily calculated through simple equations (Ettre, L.S. et al.).
  • static-coated stationary phase films need to be stabilized immediately after their coating. This is usually achieved by stationary phase immobilization through free radical cross-linking (Wright, B.W. et al.) that leads to the formation of chemical bridges between coated polymeric molecules of the stationary phase.
  • stability of the coated film is achieved not through chemical bonding of the stationary phase molecules to the capillary walls, but mainly through an increase of their molecular size and consequently, through decrease of their solubility and vapor pressure.
  • a preparation of a GC capillary column including a tube structure and a deactivated surface-bonded sol-gel coating on a portion of the tube structure forming a stationary phase was disclosed and claimed in PCT Application PCT/US99/19113, published as WO 00/11463, to Malik et al.
  • the invention disclosed therein is for a structure for forming a capillary tube, e.g., for gas chromatography, and a technique for forming such capillary tube.
  • the capillary tube includes a tube structure and a deactivated surface-bonded sol-gel coating on a portion of the tube structure to form a stationary phase coating on that portion of the tube structure.
  • the deactivated sol-gel stationary phase coating enables separation of analytes while minimizing adsorption of analytes on the separation column structure.
  • This type of column was a significant advancement in the art, but it was recognized that certain improvements would greatly enhance the performance of the sol-gel coated column.
  • a GC column is commonly operated under temperature-programmed conditions whereby the temperature of the column is increased with time. As the column temperature increases, the gas chromatography baseline rises because of column bleed caused due to the formation of volatile compounds from the stationary phase coating on the inner surface of the capillary column. In GC columns with polyslioxane-based stationary phases, the formation of volatile cyclic compounds is favored by the flexibility of the polysiloxane chains.
  • One way to overcome or significantly reduce the column-bleeding problem is to reduce the flexibility of the polymeric structure of the GC stationary phase by incorporating phenyl rings in the polysiloxane backbone.
  • This non-sol-gel process is inconvenient for two reasons. First, the process is lengthy and carried out at elevated temperature. Second, the 1 ,4-bis(hydroxydimethylsiyl)benzene reagent used for the incorporation of the phenyl group provides a polymer structure where the phenyl ring is directly bonded to silicon atoms without any spacer groups and leads to a very rigid polymer affecting its mass transfer properties and chromatographic efficiency. Accordingly, there is a need for an improved GC column having improved baseline stability, higher efficiency, and reduced conditioning time. Additionally, there is a need for a sol-gel GC column having desired stationary phase film thickness and improved retention characteristics that are capable of being fabricated into long columns. The present invention describes a sol- gel chemistry-based process that provides all of the above-mentioned desirable column characteristics through a simple procedure carried out under mild thermal conditions.
  • a capillary column including a tube structure having inner walls and a sol-gel substrate coated on a portion of the inner walls of the tube structure to form a stationary phase coating on the inner walls.
  • the sol solution used to prepare the sol-gel substrate has at least one baseline stabilizing reagent and at least one surface deactivation reagent.
  • the resulting sol-gel substrate has at least one baseline stabilizing reagent residual and at least one surface deactivation reagent residual.
  • the present invention further provides for a method of making a sol-gel solution for placement into a capillary column by mixing suitable sol-gel precursors, at least one sol-gel-active organic polymer or ligand, at least one baseline stabilization reagent to the sol-gel solution, at least one surface deactivation reagent, and at least one sol-gel catalyst.
  • Figure 1 is a longitudinal, cross-sectional view of an embodiment of a capillary column of the present invention
  • Figure 2 is drawing of an embodiment of the present invention, more specifically, a filling and purging device for the preparation of the capillary column of the present invention
  • Figure 3A GC separation of Grob test mixture on a sol-gel-coated PDMS column prepared using a sol solution containing hydroxy-term inated polydimethylsiloxane, poly dimethyl (82-86%) diphenyl (14-18%) siloxane, hydroxy-terminated poly(methylhydrosiloxane), methyltrimethoxysilane, 1 ,1 ,1 ,3,3,3,-hexamethyldisilazane, trifluoroacetic acid, and bis(tr imethoxysilylethyl)benzene, but no ammonium fluoride, wherein the conditions are: 10-m x 250- ⁇ m-i.d.
  • fused silica capillary column stationary phase, sol-gel PDMS; carrier gas, helium; injection, split (100:1 , 300 °C); detector, FID, 350 °C; temperature programming from 40 °C at 6 °C minutes "1 with peaks (1 ) 2,3-butanediol, (2) n-decane, (3) 1-octanol, (4) 1-nonanal (5) n- undecane, (6) 2,6-dimethylaniline, (7) methyl decanoate, (8) methyl undecanoate, and (9) methyl dodecanoate;
  • Figure 3B GC separation of Grob test mixture on a sol-gel-coated PDMS capillary column prepared using a sol solution containing hydroxy- terminated polydimethylsiloxane, hydroxy-terminated poly dimethyl (82-86 %) diphenyl (14-18%) siloxane, poly(methylhydrosiloxane), methyltrimethoxysilane, 1 ,1 ,1 ,3,3,3-hexamethyldisilazane, trifluoroacetic acid, and both ammonium fluoride and bis(trimethoxysilylethyl)benzene, wherein the conditions are: 10-m x 250 ⁇ m-i.d.
  • fused silica capillary column stationary phase, sol-gel PDMS; carrier gas, helium; injection, split (100:1 , 300 °C); detector, FID, 350 °C; temperature programming from 40 °C at 6 °C minutes "1 with peaks (1 ) 2,3-butanediol, (2) n-decane, (3) 1-octanol, (4) 2,6- dimethylphenol, (5) 1-nonanal, (6) n-undecane, (7) 2,6-dimethylaniline (8) methyl decanoate, (9) dicyclohexylamine, (10) methyl undecanoate and (11) methyl dodecanoate;
  • Figure 4A GC separation of Grob test mixture on a sol-gel-coated PDMS capillary column prepared using a sol solution containing hydroxy- terminated polydimethylsiloxane, hydroxy-terminated poly dimethyl (82-86%) diphenyl (14-18%) siloxane, poly(methylhydrosiloxane), methyltrimethoxysilane, 1 ,1 ,1 ,3,3,3-hexamethyldisilazane, trifluoroacetic acid, ammonium fluoride but no bis(trimethoxysilylethyl)benzene, wherein the conditions are: 10-m x 250- ⁇ m-i.d.
  • Figure 4B is a GC separation of Grob test mixture on a sol-gel-coated PDMS capillary column prepared using a sol solution containing hydroxy- terminated polydimethylsiloxane, hydroxy-terminated poly dimethyl (82-86%) diphenyl (14-18%) siloxane, poly(methylhydrosiloxane), methyltrimethoxysilane, 1 ,1 ,1 ,3,3,3-hexamethyldisilazane, trifluoroacetic acid, ammonium fluoride, and bis(trimethoxysilylethyl)benzene with conditions being 10-m x 250- ⁇ m-i.d.
  • Figure 5A is a GC separation of Grob test mixture on a sol-gel-coated PDMS capillary column prepared using a sol solution containing hydroxy- terminated polydimethylsiloxane, hydroxy-terminated poly dimethyl (82-86%) diphenyl (14-18%) siloxane, poly(methylhydrosiloxane), methyltrimethoxysilane, trifluoroacetic acid, ammonium fluoride and bis(trimethoxysilylethyl)benzene and 1 ,1 ,1 , 3,3, 3-hexamethyldisilazane, with conditions being 10-m x 250- ⁇ m-i.d.
  • fused silica capillary column stationary phase, sol-gel PDMS; carrier gas, helium; injection, split (100:1 , 300 °C); detector, FID, 350 °C; temperature programming from 40 °C at 6 °C minutes "1 , and with peaks (1 ) 2,3-butanediol, (2) n-decane, (3) 1-octanol, (4) 2,6- dimethylphenol, (5) 1 -nonanal, (6) n-undecane, (7) 2,6-dimethylaniline, (8) methyl decanoate, (9) dicyclohexylamine, (10) methyl undecanoate, and (11) methyl dodecanoate;
  • Figure 5B is a GC separation of Grob test mixture on a sol-gel-coated PDMS capillary column prepared using a sol solution containing hydroxy- terminated polydimethylsiloxane, hydroxy-terminated poly dimethyl (82-86%) diphenyl (14-18%) siloxane, poly(methylhydrosiloxane), methyltrimthoxysilane, trifluoroacetic acid, ammonium fluoride and bis(trimethoxysilylethyl)benzene but no 1 ,1 , 1 ,3,3, 3-hexamethyldisilazane, with conditions being 10-m x 250- ⁇ m-i.d.
  • fused silica capillary column stationary phase, sol-gel PDMS; carrier gas, helium; injection, split (100:1 , 300 °C); detector, FID, 350 °C; temperature programming from 40 °C at 6 °C minutes " 1 and peaks (1) 2,3-butanediol, (2) n-decane, (3) 1-octanol, (4) 2,6- dimethylphenol, (5) n-undecane, (6) 2,6-dimethylaniline, (7) methyl decanoate, (8) methyl undecanoate, and (9) methyl dodecanoate;
  • Figure 6 is a GC separation of Grob test mixture on a sol-gel-coated PDMS capillary column prepared using a sol solution containing hydroxy- terminated polydimethylsiloxane, hydroxy-terminated poly dimethyl (82-86%) diphenyl (14-18%) siloxane, poly(methylhydrosiloxane), methyltrimethoxysilane, 1 ,1 , 1 ,3, 3, 3-hexamethyldisilazane, trifluoroacetic acid, ammonium fluoride and bis(trimethoxsilylethyl)benzene, with conditions being 10-m x 250- ⁇ m-i.d.
  • fused silica capillary column stationary phase, sol-gel PDMS; carrier gas, helium; injection, split (100:1 , 300 °C); detector, FID, 350 °C; temperature programming from 40 °C at 6 °C minutes '1 ; and with peaks (1) 2,3-butanediol, (2) n-decane, (3) 1-octanol, (4) 2,6-dimethylphenol, (5) 1- nonanal, (6) n-undecane, (7) 2,6-dimethylaniline, (8) methyl decanoate, (9) dicyclohexylamine, (10) methyl undecanoate, and (11) methyl dodecanoate;
  • Figure 7 is a GC separation of PAHs on a sol-gel-coated PDMS capillary column prepared using a sol solution containing hydroxy-terminated polydimethylsiloxane, hydroxy-terminated poly dimethyl (82-86%) diphenyl (14-18%) siloxane, poly(methylhydrosiloxane), methyltrimethoxysilane, 1 ,1 ,1 ,3,3,3-hexamethyldisilazane, trifluoroacetic acid, ammonium fluoride and bis(trimethoxysilylethyl)benzene with conditions being 10-m x 250- ⁇ m-i.d.
  • fused silica capillary column stationary phase, sol-gel PDMS; carrier gas, helium; injection, split (100:1 , 300 °C); detector, FID, 350 °C, temperature programming from 80 °C at 6 °C minutes "1 and with peaks (1) naphthalene, (2) acenaphthylene, (3) acenaphthene, (4) fluorene, (5) phenanthrene, (6) o- terphenyl, (7) fluoranthene, and (8) pyrene;
  • Figure 8 is a GC separation of aniline derivatives on a sol-gel-coated PDMS capillary column prepared using a sol solution containing hydroxy- terminated polydimethylsiloxane, hydroxy-terminated poly dimethyl (82-86%) diphenyl (14-18%) siloxane, poly(methylhydrosiloxane), methyltrimethoxysilane, 1 ,1 ,1 ,3,3,3-hexamethyldisilazane, trifluoroacetic acid, ammonium fluoride and bis(trimethoxysilylethyl)benzene, with conditions being 10-m x 250- ⁇ m-i.d.
  • FIG. 9 is a gas chromatogram demonstrating separation of a Grob test mixture on a sol-gel-coated PEG column, wherein the conditions are: 10- m x 250- ⁇ m-i.d.
  • FIG. 10 is a gas chromatogram illustrating separation of aniline derivatives on a sol-gel coated PEG column, wherein the conditions are: 10-m x 250- ⁇ m-i.d.
  • Figure 11 is a gas chromatogram illustrating separation of aldehydes on a sol-gel coated PEG column, wherein the conditions are: 10-m x 250 ⁇ m- i.d. fused silica capillary column; stationary phase, sol-gel polyethylene glycol (PEG); carrier gas, helium; injection, split (100:1 , 300° C); detector, FID, 350° C; temperature programming from 75° C at 6° C min "1 ; and with peaks (1) nonylaldehyde, (2) benzaldehyde, (3) o-toulaldehyde, (4) m-toulaldehyde, and
  • Figure 12 is a gas chromatogram demonstrating separation of ketones on a sol-gel coated PEG column, wherein the conditions are: 10-m x 250- ⁇ m- i.d. fused silica capillary column; stationary phase, sol-gel polyethylene glycol (PEG); carrier gas, helium; injection, split (100:1 , 300° C); detector, FID, 350° C; temperature programming from 80° C at 6° C min "1 ; and with peaks (1) 5- . nonanone, (2) butyrophenone, (3) valerophenone, (4) hexanophenone, and (5) heptanophenone;
  • Figure 13 is a gas chromatogram illustrating separation of alcohols on a sol-gel coated PEG column, wherein the conditions are: 10-m x 250 ⁇ m-i.d. fused silica capillary column; stationary phase, sol-gel polyethylene glycol (PEG); carrier gas, helium; injection, split (100:1 , 300° C); detector, FID, 350° C; temperature programming from 70° C at 6° C min "1 ; and with peaks (1 ) butanol, (2) pentanol, (3) hexanol, (4) heptanol, and (5) octanol;
  • Figure 14 is a schematic illustration of hydrolysis reactions involved in the preparation of sol-gel PDMS coated columns according to the present invention.
  • Figure 15 is a schematic illustration of condensation reactions involved in sol-gel PDMS stationary phase of the present invention
  • Figure 16 is a schematic illustration of a condensation reaction of the present invention occurring on a fused silica capillary inner surface
  • Figure 17 is a schematic illustration of a deactivation of residual silanol groups using hexamethyldisilazane (HMDS);
  • Figure 18 is a schematic illustration of hydrolysis reactions for the preparations of sol-gel PEG coated columns according to the present invention
  • Figure 19 is a schematic illustration of a condensation reaction of the present invention demonstrating the growth of a sol-gel PEG polymer (A is a spacer group);
  • Figure 20 is a schematic illustration of a growing sol-gel PEG polymer being bonded to a silica surface
  • Figure 21 is a schematic illustration of a reaction of the sol-gel PEG polymer bonded to a silica surface with hexamethyldisilazane (HMDS) to form a deactivated sol-gel PEG polymer coating bonded to the silica surface;
  • HMDS hexamethyldisilazane
  • Figure 22 A is a scanning electron micrograph of a sol-gel PDMS coating on the inner surface of a fused silica capillary column (magnification 10,000 x);
  • Figure 22 B is a scanning electron micrograph of a sol-gel PEG coating on the inner surface of a fused silica capillary column (magnification 10,000 x).
  • the present invention is directed to a capillary column and to a method of making the capillary column, wherein the capillary column provides for a rapid and simple method for simultaneous deactivation, coating, and stationary phase immobilization in gas chromatography (hereinafter "GC").
  • GC gas chromatography
  • sol-gel chemistry-based approach to column preparation is provided that is a viable alternative to conventional GC column technology.
  • the sol-gel column technology eliminates the major drawbacks of conventional column technology through chemical bonding of the sol-gel stationary phase molecules to an interfacial layer that evolves on the top of the original capillary surface. More specifically, the present invention provides for a sol-gel GC column having improved baseline stability, higher efficiency, and reduced conditioning time.
  • the present invention further provides for a sol-gel GC column having desired stationary phase film thicknesses and improved retention characteristics that are capable of being fabricated into long columns as long as 30 meters or longer.
  • the present invention is useful for capillary systems as well as any other chromatography system that employs the use of polysiloxane-based, PEG-based, and other types of stationary phases for separation.
  • baseline stability is defined as, but is not limited to, a state wherein the formation of volatile products due to the breakdown of the stationary phase at elevated temperatures is hindered or prevented. More specifically, baseline stability occurs when the stationary phase is prevented from rearrangement so that the formation of low molecular weight compounds is suppressed. This can be achieved through a reduction of polymer chain flexibility by introducing a rigid phenyl group into the polymer backbone.
  • activation reagent as used herein is defined as, but is not limited to, any reagent that reacts with the polar adsorptive sites (e.g., silanol groups) on the column inner surface or stationary phase coating, and thereby prevents the stationary phase coating within the column from adsorbing polar analytes.
  • the adsorptive interaction of the stationary phase with polar analytes occurs because of the presence of silanol groups that are harmful to polar compounds desired to be analyzed.
  • the present invention has numerous applications and uses. Primarily, the present invention is useful in separation processes involving analytes including, but not limited, to hyrdocarbons, polycyclic aromatic hydrocarbons (PAHs), alcohols, aldehydes, ketones, phenols, fatty acids, fatty acid methyl esters, amines, and other analytes known to those of skill in the art. Accordingly, the present invention is useful in chemical, petrochemical, environmental, pharmaceutical applications, and other similar applications. The present invention has various advantages over the prior art.
  • PAHs polycyclic aromatic hydrocarbons
  • the sol-gel chemistry-based novel approach to column technology is presented for high resolution capillary GC that provides a fast way of surface roughening, deactivation, coating, and stationary phase immobilization - all carried out in a single step.
  • the new technology can achieve all these just by filling a capillary with a sol solution of appropriate composition, and allowing it to stay inside the capillary for a controlled period, followed by inert gas purging and conditioning of the capillary.
  • the new technology greatly simplifies the methodology for the preparation of high efficiency GC columns, and offers an opportunity to reduce the column preparation time at least by a factor of ten.
  • the new technology is very suitable for automation and mass production.
  • Columns prepared by the new technology provide significantly superior thermal stability due to direct chemical bonding of the stationary phase coating to the capillary walls.
  • Enhanced surface area of the columns as evidenced by SEM results, provides a sample-capacity advantage to the sol-gel columns.
  • the new methodology provides excellent surface deactivation quality, which is either comparable with or superior to that obtained by conventional techniques. This is supported by examples of high efficiency separations obtained for polar compounds including free fatty acids, amines, alcohols, diols, phenols, aldehydes and ketones.
  • the sol-gel column technology has the potential to offer a viable alternative to existing methods for column preparation in analytical microseparation techniques.
  • the present invention has numerous embodiments, depending upon the desired application. As described below, the formation of the various embodiments are intended for use in gas chromatography. However, due to the vast applicability of the present invention, the column and related methods thereof can be modified in various manners for use in other areas of analytical separation technologies. The principles of the present invention can also be used to form capillary columns for use in liquid chromatography, capillary electrochromatography, supercritical fluid chromatography, and as sample preconcentrators where a compound of interest is present in very small concentrations in a sample.
  • the present invention provides for a capillary column 10 including a tube structure 12 having inner walls 14 and a sol-gel substrate 16 coated on a portion of the inner walls 14 of the tube structure 12 to form a stationary phase coating 18 on the inner walls 14.
  • the stationary phase coating 18 is created using at least one baseline stabilizing reagent and at least one surface deactivation reagent.
  • the stationary phase coating 18 is bonded to the inner walls 14 of the tube structure 12.
  • the surface-bonded sol-gel substrate 16 is applied to the inner walls 14 of the tube structure 12 by use of an apparatus as illustrated in Figure 2 and the method described herein.
  • the tube structure 12 of the capillary column 10 can be made of numerous materials including, but not limited to alumina, fused silica, glass, titania, zirconia, polymeric hollow fibers, and any other similar tubing materials known to those of skill in the art.
  • fused silica is the most convenient material used.
  • Sol-gel chemistry in analytical microseparations presents a universal approach to creating advanced material systems including those based on alumina, titania, and zirconia that have not been adequately evaluated in conventional separation column technology.
  • the sol-gel chemistry-based column technology has the potential to effectively utilize advanced material properties to fill this gap.
  • sol-gel substrate As for the sol-gel substrate, it has the formula:
  • X Residual of a deactivation reagent (e.g., polymethylhydrosiloxane (PMHS), hexamethyldisilazane (HMDS), etc.);
  • a deactivation reagent e.g., polymethylhydrosiloxane (PMHS), hexamethyldisilazane (HMDS), etc.
  • Y Sol-gel reaction residual of a sol-gel active organic molecule (e.g., molecules with hydroxysilane or alkoxysilane monomers, polydimethylsiloxane (PDMS), polymethylphenylsiloxane (PMPS), polydimethyldiphenylsiloxane (PDMDPS), polyethylene glycol (PEG) and related polymers such as Carbowax 20M, polyalkylene glycol such as Ucon, macrocyclic molecules such as cyclodextrins, crown ethers, calixarenes, alkyl moieties such as octadecyl, octyl, a residual from a baseline stabilizing agent such as bis(trimethoxysilylethyl)benzene, 1 ,4- bis(hydroxydimethylsilyl)benzene, etc.
  • a baseline stabilizing agent such as bis(trimethoxysilylethyl)benzene, 1 ,4- bis(hydroxydi
  • Z Sol-gel precursor-forming chemical element (e.g., Si, Al, Ti,
  • I An integer > 0;
  • n An integer > 0;
  • n An integer > 0;
  • I, m, n, p, and q are not simultaneously zero.
  • sol-gel solutions In the preparation of gas chromatography columns, it is desirable to use sol-gel solutions to coat the walls of capillary tube structures for the separation of analytes.
  • sol-gels are prepared by standard methods known in the art and comprise both polysiloxane and non-polysiloxane type gels. These include, but are not limited to, polysiloxane-based gels with a wide range of substituted functional groups, including: methyl, phenyl, cyanoalkyl, cyanoaryl, etc.
  • sol-gel polyethylene glycols such as, but not limited to, PEG, Carbowax, Superox, sol-gel alkyl, sol-gel polyalkylene oxides, such as Ucon, and other sol-gels, such as sol-gel dendrimers can be modified by the instant invention.
  • the precursors utilized for preparing the sol-gel coated GC capillary columns of the present invention have the general structure of:
  • Z is the precursor-forming element taken from a group including, but not limited to, silicon, aluminum, titanium, zirconium, vanadium, germanium, and the like;
  • R ⁇ , R2, R3, and R 4 are substituent groups at least two of which are sol-gel-active, wherein the sol-gel active groups include, but are not limited to, alkoxy, hydroxy moieties, and the like.
  • Typical sol-gel-active alkoxy groups include, but are not limited to, a methoxy group, ethoxy group, n-Propoxy group, / ' so-Propoxy group, n-butoxy group, /so-butoxy group, tert- butoxy group, and any other alkoxy groups known to those of skill in the art.
  • R-groups can be any non sol-gel active groups such as methyl, octadecyl, phenyl, and the like. It is preferred however, that three or four of the R-groups are sol-gel active groups.
  • Typical non-sol-gel-active substituents of the precursor-forming element (Z) include, but are not limited to, alkyl moieties and their derivatives, alkenyl moieties and their derivatives, aryl moieties and their derivatives, arylene moieties and their derivatives, cyanoalkyl moieties and their derivatives, fluoroalkyl moieties and their derivatives, phenyl moieties and their derivatives, cyanophenyl moieties and their derivatives, biphenyl moiety and its derivatives, cyanobiphenyl moieties and their derivatives, dicyanobiphenyl moieties and their derivatives, cyclodextrin moieties and their derivatives, crown ether moieties and their derivatives, cryptand moieties and their derivatives, calixarene moieties and their derivatives, liquid crystal moieties and their derivatives, dendrimer moieties and their derivatives, cyclophane moieties and their derivatives, chir
  • precursors include, but are not limited to, a chromatographically active moiety selected from the group of octadecyl, octyl, cyanopropyl, diol, biphenyl, and phenyl.
  • Other representative precursors include, but are not limited to, Tetramethoxysilane, 3-(N-styrylmethyl-2-aminoethylamino)-propyltrimethoxysilane hydrochloride, ⁇ /-tetradecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride, N-(3- trimethoxysilylpropyl)-N-methyl-N,N-diallylammonium chloride, N- trimethoxysilylpropyltri-N-butylammonium bromide, N-trimethoxysilylpropyl- N,N,N-trimethylammonium chloride, Trimethoxysilylpropylthiouronium chloride, 3-[2-N-benzyaminoethylaminopropyl]trimethoxysilane hydrochloride, 1 ,4-Bis(hydroxydimethylsilyl)benzene, Bis(2-hydroxyethy
  • the deactivation reagents include, but is not limited to, hydrosilanes, polymethylhydrosiloxlanes, polymethylphenyl hydrosiloxanes, polymethyl cyanopropyl hydrosioloxanes, and any other similar deactivation reagent known to those of skill in the art.
  • the primary catalyst includes, but is not limited to, trifluoroacetic acid, any acid, base, fluoride, and any other similar catalyst known to those of skill in the art.
  • the performance of the sol gel stationary phase is improved by the addition of at least one baseline stabilizing reagent and at least one additional surface deactivation reagent to the sol solution.
  • the baseline-stabilizing reagent prevents rearrangement of the sol-gel polymeric stationary phase and formation of volatile compounds at elevated temperature.
  • the baseline-stabilizing reagent incorporates with the phenyl ring in the polymer backbone structure at room temperature using a sol-gel process.
  • the baseline-stabilizing reagent includes, but is not limited to, bis(trimethoxysilylethyl)-benzene (BIS), phenyl-containing groups, cyclohexane containing groups, and any other similar sol-gel active stabilizing reagent known to those of skill in the art.
  • the baseline- stabilizing reagent is used in conjunction with methyltrimethoxysilane (a sol- gel percursor), and two sol-gel catalysts (trifluoroacetic acid and ammonium fluoride). First the sol-gel reactions are carried out for ten minutes using trifluoroacetic acid as the primary catalyst.
  • a second sol-gel catalyst is used to improve the condensation process for the sol-gel coating and its bonding with the capillary inner surface.
  • the second sol-gel catalyst includes, but is not limited to, ammonium fluoride, base, fluoride, and any other similar catalysts known to those of skill in the art. It is known that under acidic conditions the hydrolysis reaction proceeds faster to produce primarily linear polymeric structure, but the polycondensation reaction remains slow. The addition of fluoride increases the polycondensation reaction rate.
  • a surface derivatization reagent is added as a secondary deactivation reagent, which includes, but is not limited to, 1 ,1 ,1 ,3,3,3- heaxmethyldisilazane, any hydrosilane, and any other similar surface deactivation reagents known to those of skill in the art.
  • sol-gel reactions involved in the formation of the polysiloxane structure described herein, incorporation of phenyl ring, and chemical bonding of the polymer to the column inner walls are illustrated in Figures 14-21 for sol-gel PDMS and sol- gel PEG.
  • the preparation of the sol-gel coating includes the steps of providing the tube structure, providing a sol-gel solution including one or more sol-gel precursors, an organic material with at least one sol-gel active functional group, one or more sol-gel catalysts, one or more deactivation reagents, and a solvent system.
  • the sol-gel solution is then reacted with a portion of the tube (e.g., inner surface) under controlled conditions to produce a surface bonded sol-gel coating on the portion of the tube.
  • the free portion of the solution is then removed from the tube under pressure, purged with an inert gas, and is heated under controlled conditions to cause the deactivation reagent to react with the surface bonded sol-gel coating to deactivate and to condition the sol-gel coated portion of the tube structure.
  • the sol- gel precursor includes an alkoxy compound.
  • the organic material includes a monomeric or polymeric material with at least one sol-gel active functional group.
  • the sol-gel catalyst is taken from the group consisting of an acid, a base and a fluoride compound, and the deactivation reagent includes a material reactive to polar functional groups (e.g., hydroxyl groups) bonded to the sol-gel precursor-forming element in the coating or to the tube structure.
  • the specific steps for fabrication starts with the cleaning and hydrothermal treatment of a fused silica capillary. Then, the preparation of the sol-gel solution utilizing the above precursors is done. Next, the inner walls of the hydrothermally treated capillary column are coated with the prepared sol-gel solution. Finally, conditioning of the sol-gel coated capillary tube is performed.
  • the device 20 includes a metallic cylindrical pressurization chamber 22 and a bottom cap 24.
  • the bottom cap is removably attached to a distal end thereof by a screw-threaded portion 34. It is understood that any attachment mechanism can be used to secure the bottom cap 24 to the distal portion of the chamber 22.
  • a proximal end of the chamber 22 has a second sealing mechanism 36 with an outlet mechanism 26, generally in the form of a cross or any other suitable shape as desired, extending therefrom.
  • This outlet mechanism 26 has outwardly extending portions 38, 40, 42 with outlet valves 28, 30 contained within the radially extending portions or arms thereof.
  • the upwardly extending portion of the outlet means 26 has a capillary column 10 extending therefrom, which is removably inserted through the upwardly extending arm of the outlet device.
  • the sol-gel solution of the present invention utilizes various sol-gel precursors.
  • the sol-gel solution is prepared by mixing two solutions together that are each prepared in separate polypropylene vials.
  • the first solution contains hydroxy-terminated polydimethylsiloxane (PDMS), hydroxy-terminated polydimethyldiphenylsiloxane (PDMDPS), polymethylhydrosiloxane (PMHS) and methylene chloride.
  • the second solution is methyltrimethoxysilane, bis(trimethoxysilylethyl)-benzene, 1 ,1 , 1 ,3,3, 3-hexamethyldisilazane (HMDS) and methylene chloride.
  • airtight sealing mechanism 44 is in communication with the arm member extending upwardly from the cross-like member and connecting means 46 extending from the radially extending arms.
  • the valves 28, 30 Prior to the insertion of the vial 32 into the chamber 22, the valves 28, 30 are closed and then the capillary column 10 is inserted into the chamber 22 via the outwardly extending portion of the cross-like member 26 such that it is in contact with the sol-gel solution contained in vial 32.
  • a gas pressure is selected depending on the size of the capillary to be filled and this pressure is applied to an inert gas applied to the chamber 22 by opening the valve 28.
  • the sol-gel is then pushed up from the vial 32 into the capillary 10, completely filling the extent thereof.
  • the inlet valve 28 is closed and the outlet valve 30 is then opened to release the excess pressure from the chamber 22.
  • the solution is allowed to reside inside the full extent of the capillary column 10 for a desired length of time, according to the thickness of coating to be formed on the inner walls 14 of the tube structure 12 of the capillary column 10, and the sol-gel reactions take place within the capillary column 10.
  • These reactions include chemical bonding of the inner walls 14 of the tube structure 12 with the components of the sol-gel by virtue of the silanol groups in the polymeric network reacting with the silanol groups of the silica tube structure 12.
  • This reaction forms an immobilized sol-gel surface coating integral with the inner walls 14 of the tube structure 12.
  • the now filled capillary is then subjected to further processing.
  • the outlet valve 30 is closed and the inlet valve 28 is opened to allow for an inert pressurized gas to be again introduced into the capillary 10.
  • the cap 24 Prior to this gas introduction, the cap 24 is opened to remove the vial 32, leaving the chamber 22 without any members other than the distal end of capillary 10 extending thereto.
  • This gas purging allows the excess sol-gel solution, which has not yet bonded to the capillary walls to be purged from the capillary 10 via its distal end. Purging with the inert gas also removes any residual solvent or other volatiles from the capillary 10.
  • Final conditioning of the capillary 12 is accomplished by sealing the ends of the capillary after it is removed from the device 20 by use of any known sealing means such as an oxy-acetylene torch. A programmed system of heating is then applied to the capillary and then the seals are removed to allow for solvent rinsing after which a final programmed temperature drying with simultaneous inert gas purging is performed. The column thus prepared is ready then for use.
  • any known sealing means such as an oxy-acetylene torch.
  • Fused silica capillary 250 ⁇ m i.d.
  • Polymicro Technologies Inc. Panoenix, AZ, USA
  • HPLC-Grade tetrahydrofuran (THF), methylene chloride, and methanol were purchased from Fisher Scientific (Pittsburgh, PA, USA).
  • Tetramethoxysilane 99 + %, poly(methylhydrosiloxane) (PMHS), and trifluoroacetic acid (containing 5% water), were purchased from Aldrich (Milwaukee, Wl, USA) Hydroxy- terminated poly(dimethylsiloxane) (PDMS), methyl-trimethoxysilane (MTMS) and t methylmethoxysilane (TMMS) were purchased from United Chemical Technologies, Inc. (Bristol, PA, USA). Ucon 75-H-90,000 polymer was obtained from Alltech (Deerfield, IL, USA).
  • (c) deionized water (c) deionized water.
  • the capillary is then purged with a flow of helium, or any other inert gas, for 5 minutes leaving behind a thin coating of deionized water on the inner surface of the capillary.
  • the two ends of the capillary are then sealed with an oxy- acetylene flame.
  • the sealed capillary was then heated by programming the temperatures from an initial value of 40° C to a final value of 300° C at a rate of change of 4° C per minute, and allowing the thermal treatment at the final temperature to continue for approximately 120 minutes.
  • the capillary was allowed to cool down to room temperature, and then the ends are cut open.
  • the capillary was then purged again with an inert gas, the flow rate being 1 ml per minute while being simultaneously heated at the same programmed temperature as delineated before.
  • Solution 1 (a) Hydroxy-terminated Polydimethylsiloxane (PDMS)
  • sol-gel polymer This allowed the sol-gel polymer to be formed in the sol solution and get bonded to the inner walls of the capillary.
  • the excess, unreacted sol-gel solution was then expelled from the capillary under helium or other inert gas pressure, leaving the surface-bonded coating on the inner surface of the capillary tube. Volatiles and residual solvents or sol-gel solution were then purged off the tube using helium or other inert gas for 30-60 minutes.
  • Optimized Solution Solution 1

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Abstract

La présente invention concerne un capillaire (10) comportant une structure tubulaire présentant des parois internes (14) et un substrat de sol-gel (16) revêtu sur une portion des parois internes (14) en vue de former un revêtement de phase stationnaire (18) sur les parois internes (14). La solution de sol utilisée pour la préparation du substrat sol-gel (16) présente au moins un réactif stabilisateur de départ et au moins un réactif de désactivation superficielle avec pour conséquence la présence d'au moins un résidu de réactif stabilisateur de départ et au moins un résidu de réactif de désactivation superficielle dans le substrat sol-gel (16). L'invention concerne également un procédé de préparation de la solution de sol-gel qui consiste à mélanger des précurseurs pour former la solution, la stabilisation de la solution en y ajoutant un réactif stabilisateur de départ, la désactivation de la solution en y ajoutant au moins un réactif de désactivation superficielle à la solution, et à faire réagir la solution en présence d'au moins un catalyseur.
PCT/US2002/007163 2001-03-09 2002-03-08 Colonne de chromatographie sol-gel a grande efficacite WO2002072225A1 (fr)

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EP1630190A2 (fr) * 2004-08-05 2006-03-01 Agilent Technologies, Inc. Composés de polyhydrosiloxane, produits et leur utilisation
US7947174B2 (en) 2000-02-09 2011-05-24 University Of South Florida Sol-gel monolithic column with optical window and method of making
US8323504B2 (en) 2010-11-16 2012-12-04 Nobull Innovation Llc Methods and apparatus for making a chromatography column
US8329038B2 (en) 2010-11-16 2012-12-11 Nobull Innovation Llc Methods and apparatus for making a chromatography column
US8377309B2 (en) 2010-11-16 2013-02-19 Nobull Innovation Llc Methods and apparatus for making a chromatography column
US8685240B2 (en) 2001-03-09 2014-04-01 University Of South Florida High efficiency sol-gel gas chromatography column
CN108169503A (zh) * 2018-01-12 2018-06-15 河北工业大学 基于微流控芯片的芳香族挥发性气体快速检测系统
CN113433248A (zh) * 2021-07-19 2021-09-24 北京科瑞麦科技有限公司 气相色谱柱的制备方法及具有该色谱柱的色谱仪装置

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US7947174B2 (en) 2000-02-09 2011-05-24 University Of South Florida Sol-gel monolithic column with optical window and method of making
US8597508B2 (en) 2000-02-09 2013-12-03 University Of South Florida Sol-gel monolithic column with optical window and method of making
US8685240B2 (en) 2001-03-09 2014-04-01 University Of South Florida High efficiency sol-gel gas chromatography column
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US8329038B2 (en) 2010-11-16 2012-12-11 Nobull Innovation Llc Methods and apparatus for making a chromatography column
US8323504B2 (en) 2010-11-16 2012-12-04 Nobull Innovation Llc Methods and apparatus for making a chromatography column
CN108169503A (zh) * 2018-01-12 2018-06-15 河北工业大学 基于微流控芯片的芳香族挥发性气体快速检测系统
CN108169503B (zh) * 2018-01-12 2024-02-02 河北工业大学 基于微流控芯片的芳香族挥发性气体快速检测系统
CN113433248A (zh) * 2021-07-19 2021-09-24 北京科瑞麦科技有限公司 气相色谱柱的制备方法及具有该色谱柱的色谱仪装置
CN113433248B (zh) * 2021-07-19 2022-02-08 北京科瑞麦科技有限公司 气相色谱柱的制备方法及具有该色谱柱的色谱仪装置

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