US20160158728A1 - Modified diamond particles - Google Patents

Modified diamond particles Download PDF

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US20160158728A1
US20160158728A1 US15/040,771 US201615040771A US2016158728A1 US 20160158728 A1 US20160158728 A1 US 20160158728A1 US 201615040771 A US201615040771 A US 201615040771A US 2016158728 A1 US2016158728 A1 US 2016158728A1
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separation apparatus
chemical separation
derivative
isocyanate
acyl halide
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Matthew R. Linford
Landon A. Wiest
David Jensen
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Brigham Young University
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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
    • B01J20/3244—Non-macromolecular compounds
    • B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
    • B01J20/3248—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
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    • 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
    • B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
    • B01J20/3248—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such
    • B01J20/3251—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such comprising at least two different types of heteroatoms selected from nitrogen, oxygen or sulphur
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    • 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
    • B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
    • B01J20/3248—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such
    • B01J20/3253—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such comprising a cyclic structure not containing any of the heteroatoms nitrogen, oxygen or sulfur, e.g. aromatic structures
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/40—Concentrating samples
    • G01N1/405—Concentrating samples by adsorption or absorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B01D15/34—Size selective separation, e.g. size exclusion chromatography, gel filtration, permeation
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • 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
    • 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
    • B01D15/38—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving specific interaction not covered by one or more of groups B01D15/265 - B01D15/36
    • B01D15/3804—Affinity chromatography
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated

Definitions

  • silica based stationary phases have dominated the world of chemical separations.
  • silica has certain limitations. Under acidic conditions, silica tends to lose its functionality and under basic conditions it dissolves entirely after a matter of hours. Not until recently have alternatives to silica been available such as polymer based stationary phases. These tend to swell when exposed to organic solvents and are therefore not ideal for reversed-phase separations.
  • Chemists have worked around the limitations of available stationary phases, but these workarounds often result in less than ideal outcomes. For instance, certain separations may need to occur under basic or acidic conditions because the analyte of interest may only be stable under a certain pH range. It is would therefore be ideal to find a phase that could perform a separation under extreme pHs that current phases cannot successfully do separations at.
  • Diamond has usually been assumed to be inert and relatively little has been done to investigate the possibility of diamond as the basis for a stationary phase.
  • Nosterenko et al. has performed separations of proteins using oxidized/cleaned diamond and Saini et al. has been successful in coating the diamond surface with poly(allylamine). This coated diamond was then used as a normal phase in Solid-phase Extraction (SPE).
  • SPE Solid-phase Extraction
  • Saini's study also showed that his phase was extremely stable under extreme pH conditions (from pH 0-pH 14) for 24 h.
  • the SPE column was able to be reused many times and showed no signs of degradation. It also performed in the same manner experiment after experiment and only required a flush with ethyl acetate in between uses.
  • a new phase is directly bonded to the diamond surface which has been largely hydroxyl terminated.
  • diamond cleaned with piranha solution is treated with lithium aluminum hydride (LAH).
  • LAH lithium aluminum hydride
  • This reaction greatly increases the amount of hydroxyl groups on the diamond surface. Since hydroxyl groups are reactive to various functional groups, this chemistry is exploited to attach ligands directly to the diamond surface.
  • isocyanates and acyl halides (primarily Br and CI) are reactive to the hydroxyl functional group and form urethane and ester linkages respectively, that are directly bonded to the diamond surface. (See FIG. 1 )
  • Bases do have the ability to hydrolyze this linkage at the carbonyl site, so bulky groups (methyl, isopropyl, tert-butyl, phenyl etc.) can be attached to the ⁇ -carbon of the ligand to sterically hinder the binding site and prevent bases from accessing the partially negative carbon. This should give this type of linkage greater stability in the presence of acids and bases.
  • the reusability and consistency of the column is also expected to be similar to that of Saini's column and this chemistry can be applied to HPLC and SPE stationary phases.
  • An aspect is a method for preparing modified diamond particles for use in chromatography where hydroxyl groups at the diamond surfaces are reacted with a reactive molecule to introduce a desired functional group at the diamond surface.
  • An example is the reaction of Isocyanates and acyl halides with hydroxyl-terminated diamond to form HPLC/SPE stationary phases.
  • Another aspect is a method for preparing modified diamond particles for use in chromatography where i) diamond particles are reacted with an oxidizing agent that introduces carboxyl groups at the surface of the diamond, ii) the carboxyl groups are reduced to primary alcohols, and iii) the primary alcohols are reacted with a reactive molecule to introduce a desired functional group at the diamond surface.
  • the diamond particles of the present method can be used in any suitable type of chromatography type. These include, for example, high performance liquid chromatography (HPLC), ultra performance liquid chromatography (UPLC), solid phase extraction, electrochromatography, size-exclusion chromatography, ion chromatography, affinity chromatography.
  • HPLC high performance liquid chromatography
  • UPLC ultra performance liquid chromatography
  • solid phase extraction electrochromatography
  • electrochromatography size-exclusion chromatography
  • ion chromatography ion chromatography
  • affinity chromatography affinity chromatography
  • the chromatography may be practiced at any suitable pressure, such as for example, between 1000 psi and 15000 psi.
  • the diamond surface may be prepared by reducing the surface with a suitable reducing agent prior to reaction with the reactive molecule.
  • a suitable reducing agent is contemplated, such as, for example, lithium aluminum hydride.
  • the reactive function group may be any suitable functional group with the desired reactivity, and may have attached to the reactive group an alkyl group or aryl group.
  • the alkyl group may be branched or unbranched.
  • the alkyl group may be partially or fully fluorinated,
  • the aryl group may have the form —C 6 H 6 .
  • the aryl group may be partially or fully fluorinated.
  • Examples of the reactive functional groups include, one of or a mixture of an alkyl isocyanate, an aryl isocyanate, an acid chloride with an aromatic group, an acid chloride with an alkyl group, an acid bromide, an alkyl halide, an aryl halide, a benzyl halide, a benzyl triflate, a benzyl mesylate, an alkyl mesylate, an alkyl tosylate, and an alkyl triflate.
  • the reactive functional group may contain more than one other group near the reactive site of the molecule, which provides steric hindrance for the adsorbed species.
  • the reactive molecule may contain C—H bonds.
  • the reactive molecule may contain an electrophilic site and a leaving group.
  • Another aspect is a diamond particle for use in chromatography containing groups tethered to the diamond surface through ether, ester, or urethane linkages.
  • FIG. 1 Scheme outlining basic chemistry for the formation of the isocyanate and acyl halide reacted diamond particles
  • FIG. 2 Spectra confirming the step by step synthesis of a carbamide linked C 18 chain to the diamond surface
  • FIG. 3 Possible examples of the types of groups attached at the ⁇ -carbon site to increase sterics of the area in order to prevent nucleophilic attack of a base at the carbonyl resulting in hydrolysis of the ether or urethane linkage.
  • Micro-diamond or diamond powder is treated with piranha solution (3:7 30% H 2 O 2 :conc. H 2 SO 4 ) or any other suitable cleaning/etching solution. This cleans/etches the diamond surface and exposes the various functional groups that naturally occur on the diamond surface.
  • the diamond must be dried thoroughly before the next step. This can be performed by pulling argon through the powder or placing the powder in a vacuum for many hours. The dryness can be verified by diffuse reflectance infrared Fourier transform (DRIFT).
  • DRIFT diffuse reflectance infrared Fourier transform
  • LAH LiAlH 4
  • THF or any other strongly reducing base
  • LAH is extremely reactive to water.
  • the reaction must be performed under inert atmosphere (argon) and all glassware must be dry.
  • the reaction is quenched by 1M HCl. This should be added very slowly due to the reactivity of LAH with water and HCl.
  • the diamond is filtered over a fine fritted Buchner funnel and washed with copious amounts of water. If white particles are present, rinse with more 1 M HCl to dissolved the reacted LAH. Once thoroughly rinsed, the powder is dried completely. This gives hydroxyl terminated diamond.
  • Another US patent [2] discloses powders “attached with hydrocarbon, amino, carboxylic acid, or sulfonic acid groups.”
  • the present method is specifically targeting the reaction of the hydroxylated surface with a reactive molecule to introduce a desired functional group at the diamond surface, such as, for example, reactive isocyanates and acyl halides, and this chemistry and these functional groups are not disclosed.
  • the hydroxyl terminated diamond is then placed in a reaction vessel which is subsequently flushed with inert atmosphere. Then a reactive molecule is added to the powder.
  • a desired isocyanate or acyl halide is added to the powder (about 0.5 mL:1 g hydroxyl terminated diamond) then add enough dry tetrahydrofuran (THF) or ether to completely dissolve the isocyanate or acyl halide.
  • THF dry tetrahydrofuran
  • the reaction should then react for at least 18 h at room temperature. Filter the diamond over a fine fritted Buchner funnel and wash with a large amount of THF or ether to rinse away the unreacted isocyanate or acyl halide. Dry the powder completely.
  • the powder is then suspended in a solvent and pressed into an HPLC column.
  • the ToF-SIMS data shows an increase of hydrocarbon fragments in the positive ion spectra and a decrease of 0 (16 m/z) and OH (17 m/z) fragments in the negative ion spectra. This result is predicted because fewer O and OH groups would be exposed on the diamond surface once the isocyanate group has reacted with the OH functional group.
  • the XPS spectrum shows the presence of nitrogen which is absent from the piranha and LAH treated diamond powders. The only source of nitrogen in this experiment is from the isocyanate group. This therefore further confirms the formation of the carbamide linkage on the diamond surface.
  • an HPLC column is packed with 5 ⁇ m octadecyl isocyanate reacted diamond powder. If non-porous diamond is used, few plates are expected to be present on the column. This should be remedied by using porous diamond powder.
  • the chemistry of the present method is expected to work with various isocyanates and acyl halides, including compounds with the disubstituted ⁇ -carbons (see FIG. 3 for some examples).
  • the acyl halide derivatives of these compounds would also be used including the tert-butyl group not shown in the figure.
  • Other functional groups past the functionalized ⁇ -carbon could include but are not limited to phenyl, naphthyl, chiral, perfluorinated, C 8 , and C 10 .

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Abstract

Modified diamond particles for use in chromatography with a desired functional group at the diamond surface, formed from reaction of hydroxyl groups at diamond surfaces with a reactive molecule.

Description

    CROSS REFERENCE TO RELATED APPLICATIONS
  • This application is a continuation of U.S. patent application Ser. No. 13/526,410, filed 18 Jun. 2012, which is a divisional of U.S. patent application Ser. No. 12/557,503, filed 10 Sep. 2009, which claims priority from U.S. Provisional Patent Application 61/191,692, filed 10 Sep. 2008, the disclosure of each of the foregoing applications is hereby incorporated by this reference.
    • BACKGROUND
  • Since the inception of modern chromatography, silica based stationary phases have dominated the world of chemical separations. Unfortunately, silica has certain limitations. Under acidic conditions, silica tends to lose its functionality and under basic conditions it dissolves entirely after a matter of hours. Not until recently have alternatives to silica been available such as polymer based stationary phases. These tend to swell when exposed to organic solvents and are therefore not ideal for reversed-phase separations.
  • Chemists have worked around the limitations of available stationary phases, but these workarounds often result in less than ideal outcomes. For instance, certain separations may need to occur under basic or acidic conditions because the analyte of interest may only be stable under a certain pH range. It is would therefore be ideal to find a phase that could perform a separation under extreme pHs that current phases cannot successfully do separations at.
  • Diamond has usually been assumed to be inert and relatively little has been done to investigate the possibility of diamond as the basis for a stationary phase. Nosterenko et al. has performed separations of proteins using oxidized/cleaned diamond and Saini et al. has been successful in coating the diamond surface with poly(allylamine). This coated diamond was then used as a normal phase in Solid-phase Extraction (SPE). Saini's study also showed that his phase was extremely stable under extreme pH conditions (from pH 0-pH 14) for 24 h. The SPE column was able to be reused many times and showed no signs of degradation. It also performed in the same manner experiment after experiment and only required a flush with ethyl acetate in between uses.
  • These two groups have shown that separations can indeed be performed with diamond as the basis for a stationary phase. Nesterenko's study lacked good resolution in it HPLC spectra and Saini's capacity was quite low, but efforts are being made to remedy the capacity issue.
    • CITED REFERENCES
  • [1] US Patent 20050189279
  • [2] US Patent 20040118762
    • SUMMARY
  • A new phase is directly bonded to the diamond surface which has been largely hydroxyl terminated. In a specific example, diamond cleaned with piranha solution is treated with lithium aluminum hydride (LAH). This reaction greatly increases the amount of hydroxyl groups on the diamond surface. Since hydroxyl groups are reactive to various functional groups, this chemistry is exploited to attach ligands directly to the diamond surface. For example, isocyanates and acyl halides (primarily Br and CI) are reactive to the hydroxyl functional group and form urethane and ester linkages respectively, that are directly bonded to the diamond surface. (See FIG. 1)
  • Bases do have the ability to hydrolyze this linkage at the carbonyl site, so bulky groups (methyl, isopropyl, tert-butyl, phenyl etc.) can be attached to the α-carbon of the ligand to sterically hinder the binding site and prevent bases from accessing the partially negative carbon. This should give this type of linkage greater stability in the presence of acids and bases. The reusability and consistency of the column is also expected to be similar to that of Saini's column and this chemistry can be applied to HPLC and SPE stationary phases.
  • An aspect is a method for preparing modified diamond particles for use in chromatography where hydroxyl groups at the diamond surfaces are reacted with a reactive molecule to introduce a desired functional group at the diamond surface. An example is the reaction of Isocyanates and acyl halides with hydroxyl-terminated diamond to form HPLC/SPE stationary phases.
  • Another aspect is a method for preparing modified diamond particles for use in chromatography where i) diamond particles are reacted with an oxidizing agent that introduces carboxyl groups at the surface of the diamond, ii) the carboxyl groups are reduced to primary alcohols, and iii) the primary alcohols are reacted with a reactive molecule to introduce a desired functional group at the diamond surface.
  • The diamond particles of the present method can be used in any suitable type of chromatography type. These include, for example, high performance liquid chromatography (HPLC), ultra performance liquid chromatography (UPLC), solid phase extraction, electrochromatography, size-exclusion chromatography, ion chromatography, affinity chromatography.
  • The chromatography may be practiced at any suitable pressure, such as for example, between 1000 psi and 15000 psi.
  • The diamond surface may be prepared by reducing the surface with a suitable reducing agent prior to reaction with the reactive molecule. Any suitable reducing agent is contemplated, such as, for example, lithium aluminum hydride.
  • The reactive function group may be any suitable functional group with the desired reactivity, and may have attached to the reactive group an alkyl group or aryl group. The alkyl group may have the form —(CH2)nCH3, where n=0-25. The alkyl group may be branched or unbranched. The alkyl group may be partially or fully fluorinated, The aryl group may have the form —C6H6. The aryl group may be partially or fully fluorinated.
  • Examples of the reactive functional groups include, one of or a mixture of an alkyl isocyanate, an aryl isocyanate, an acid chloride with an aromatic group, an acid chloride with an alkyl group, an acid bromide, an alkyl halide, an aryl halide, a benzyl halide, a benzyl triflate, a benzyl mesylate, an alkyl mesylate, an alkyl tosylate, and an alkyl triflate.
  • The reactive functional group may contain more than one other group near the reactive site of the molecule, which provides steric hindrance for the adsorbed species.
  • The reactive molecule may contain C—H bonds. The reactive molecule may contain an electrophilic site and a leaving group.
  • Another aspect is a diamond particle for use in chromatography containing groups tethered to the diamond surface through ether, ester, or urethane linkages.
    • BRIEF DESCRIPTION OF DRAWINGS
  • FIG. 1: Scheme outlining basic chemistry for the formation of the isocyanate and acyl halide reacted diamond particles
  • FIG. 2: Spectra confirming the step by step synthesis of a carbamide linked C18 chain to the diamond surface
  • FIG. 3: Possible examples of the types of groups attached at the α-carbon site to increase sterics of the area in order to prevent nucleophilic attack of a base at the carbonyl resulting in hydrolysis of the ether or urethane linkage.
    •  DETAILED DESCRIPTION Example Experimental
  • Micro-diamond or diamond powder is treated with piranha solution (3:7 30% H2O2:conc. H2SO4) or any other suitable cleaning/etching solution. This cleans/etches the diamond surface and exposes the various functional groups that naturally occur on the diamond surface. The diamond must be dried thoroughly before the next step. This can be performed by pulling argon through the powder or placing the powder in a vacuum for many hours. The dryness can be verified by diffuse reflectance infrared Fourier transform (DRIFT).
  • The cleaned dry diamond is then treated with 1M LiAlH4 (LAH) suspended in THF (or any other strongly reducing base) [1] for 24-68 h at room temperature (about 1 g diamond:5 mL LAH solution). Warning: LAH is extremely reactive to water. Use proper PPE. The reaction must be performed under inert atmosphere (argon) and all glassware must be dry. The reaction is quenched by 1M HCl. This should be added very slowly due to the reactivity of LAH with water and HCl. Once the reaction is quenched, the diamond is filtered over a fine fritted Buchner funnel and washed with copious amounts of water. If white particles are present, rinse with more 1 M HCl to dissolved the reacted LAH. Once thoroughly rinsed, the powder is dried completely. This gives hydroxyl terminated diamond.
  • The reduced surface has been disclosed US patent [1], the reaction of the hydroxylated surface with various functional groups is not disclosed. The present method is an improvement over the disclosed diamond-based chromatographic processes.
  • Another US patent [2] discloses powders “attached with hydrocarbon, amino, carboxylic acid, or sulfonic acid groups.” The present method is specifically targeting the reaction of the hydroxylated surface with a reactive molecule to introduce a desired functional group at the diamond surface, such as, for example, reactive isocyanates and acyl halides, and this chemistry and these functional groups are not disclosed.
  • In a specific example, for this final step the hydroxyl terminated diamond is then placed in a reaction vessel which is subsequently flushed with inert atmosphere. Then a reactive molecule is added to the powder. For example, a desired isocyanate or acyl halide is added to the powder (about 0.5 mL:1 g hydroxyl terminated diamond) then add enough dry tetrahydrofuran (THF) or ether to completely dissolve the isocyanate or acyl halide. The reaction should then react for at least 18 h at room temperature. Filter the diamond over a fine fritted Buchner funnel and wash with a large amount of THF or ether to rinse away the unreacted isocyanate or acyl halide. Dry the powder completely. The powder is then suspended in a solvent and pressed into an HPLC column.
  • Results and Discussion
  • Thus far, only octadecyl isocyanate has been reacted with the hydroxyl terminated diamond. The evidence of the successive reactions can be seen in FIG. 2 by the DRIFT, ToF-SIMS and XPS spectra. There is a decrease in the height of the alcohol peak (3500 cm−1) seen in the octadecyl isocyanate DRIFT spectrum as compared to the LAH spectrum. It is clear that not all of the alcohol functional groups are reacted and this is attributed to the steric hindrance of the diamond surface. The 2° amine peak at 3342.43 cm−1, asymmetric and symmetric C—H stretches at 2920.95 cm−1 and 2848.21 cm−1 and the carbonyl stretches at 1612.33 cm−1 and 1572.64 cm−1 are indicative of successful bonding of octadecyl isocyanate to the hydroxyl terminated surface as evidenced by the urethane (carbamide) linkage.
  • The ToF-SIMS data shows an increase of hydrocarbon fragments in the positive ion spectra and a decrease of 0 (16 m/z) and OH (17 m/z) fragments in the negative ion spectra. This result is predicted because fewer O and OH groups would be exposed on the diamond surface once the isocyanate group has reacted with the OH functional group. The XPS spectrum shows the presence of nitrogen which is absent from the piranha and LAH treated diamond powders. The only source of nitrogen in this experiment is from the isocyanate group. This therefore further confirms the formation of the carbamide linkage on the diamond surface.
  • In another embodiment, an HPLC column is packed with 5 μm octadecyl isocyanate reacted diamond powder. If non-porous diamond is used, few plates are expected to be present on the column. This should be remedied by using porous diamond powder.
  • The chemistry of the present method is expected to work with various isocyanates and acyl halides, including compounds with the disubstituted α-carbons (see FIG. 3 for some examples). The acyl halide derivatives of these compounds would also be used including the tert-butyl group not shown in the figure. Other functional groups past the functionalized α-carbon could include but are not limited to phenyl, naphthyl, chiral, perfluorinated, C8, and C10.
    • CONCLUSION
  • The chemistry for creating urethane (carbamide) linkages to the diamond surface is straight forward and should prove useful in the creation of diamond-based HPLC and SPE stationary phases. The attachment of octadecyl isocyanate to the diamond surface has been verified and other isocyanates/acyl halides should also react in a similar manner to the hydroxyl terminated diamond surface.
  • Once a diamond-based HPLC column is successfully created and used, the added stability, reusability and consistency of these diamond columns will exceed that of its similarly functionalize silica-based counterparts. This strength comes from the urethane and/or ester linkages which bind the diamond and the functional group together. This will result in greater stability at more extreme pHs and the disubstituted α-carbon should help increase the stability further in basic conditions.
  • While invention has been described with reference to certain specific embodiments and examples, it will be recognized by those skilled in the art that many variations are possible without departing from its scope and spirit, and that any invention, as described by the claims, is intended to cover all changes and modifications that do not depart from the spirit of the invention.

Claims (20)

What is claimed is:
1. A chemical separation apparatus, comprising:
a stationary phase including a plurality of diamond surfaces, each of at least some of the plurality of diamond surfaces including a modified surface having at least one of an acyl halide derivative or an isocyanate derivative tethered to the modified surface through an ester linkage or a urethane linkage respectively.
2. The chemical separation apparatus of claim 1 wherein the at least one of the acyl halide derivative or the isocyanate derivative provides steric hindrance from further reactions with at least one of the diamond surface, the ester linkage, or the urethane linkage.
3. The chemical separation apparatus of claim 1 wherein the acyl halide or the isocyanate derivative is formed from an acyl halide molecule or an isocyanate molecule having an electrophilic site.
4. The chemical separation apparatus of claim 1 wherein the acyl halide derivative or the isocyanate derivatives is formed from an acyl halide or isocyanate molecule having a leaving group.
5. The chemical separation apparatus of claim 1 wherein the acyl halide derivative or the isocyanate derivative is a reaction product of one or more of alkyl isocyanate, aryl isocyanate, acid chloride with aromatic group, acid chloride with alkyl group, or acid bromide.
6. The chemical separation apparatus of claim 1 wherein the acyl halide derivative or the isocyanate derivative includes one of or more of alkyl groups or aryl groups.
7. The chemical separation apparatus of claim 6 wherein the acyl halide derivative or the isocyanate derivative includes an alkyl group with the formula —(CH2)nCH3, where n=0-25.
8. The chemical separation apparatus of claim 6 wherein the acyl halide derivative or the isocyanate derivative includes an alkyl group that is branched.
9. The chemical separation apparatus of claim 8 wherein the alkyl group is branched after an α-carbon of the acyl halide or isocyanate derivatives.
10. The chemical separation apparatus of claim 6 wherein the acyl halide or isocyanate derivative is branched at an α-carbon thereof.
11. The chemical separation apparatus of claim 6 wherein the acyl halide derivative or the isocyanate derivative include an alkyl group that is partially or fully fluorinated.
12. The chemical separation apparatus of claim 6 wherein the acyl halide derivative or the isocyanate derivative includes an aryl group that is partially or fully fluorinated.
13. The chemical separation apparatus of claim 1 wherein the plurality of diamond particles are porous diamond particles.
14. The chemical separation apparatus of claim 1 wherein the at least one of the acyl halide derivative or the isocyanate derivative includes one or more functional groups near enough to the ester linkage or the urethane linkage effective to provide steric hindrance for further reactions at the diamond surface.
15. The chemical separation apparatus of claim 1 wherein the chemical separation apparatus is configured as a solid phase extraction column.
16. The chemical separation apparatus of claim 1 wherein the chemical separation apparatus is configured as a chromatography column.
17. The chemical separation apparatus of claim 16 wherein the chromatography column is configured as a high-performance liquid chromatography column, ultra-performance chromatography column, a gel filtration column, an ion exchange column, or an affinity separation column.
18. A chemical separation apparatus, comprising:
a stationary phase including a plurality of diamond surfaces, each of at least some of the plurality of diamond surfaces including a modified surface having at least one acyl halide derivative tethered to the modified surface through an ester linkage.
19. A method of separating an analyte, the method comprising:
disposing a solution containing an analyte in a chemical separation apparatus, the chemical separation apparatus including a stationary phase including a plurality of diamond surfaces, each of at least some of the plurality of diamond surfaces including a modified surface having at least one of an acyl halide derivative or an isocyanate derivative tethered to the modified surface through an ester linkage or a urethane linkage respectively; and
separating the analyte from the solution with the chemical separation apparatus.
20. The method of claim 19 wherein the at least one of the acyl halide derivative or the isocyanate derivative provide steric hindrance from further reactions with at least one of the diamond surface, the ester linkage, or the urethane linkage.
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WO2010034027A1 (en) * 2008-09-22 2010-03-25 Brigham Young University Functionalization of hydrogen deuterium-terminated diamond
US8784520B2 (en) * 2011-06-30 2014-07-22 Baker Hughes Incorporated Methods of functionalizing microscale diamond particles
US9938771B2 (en) 2014-11-03 2018-04-10 Baker Hughes, A Ge Company, Llc Initiator nanoconstituents for elastomer crosslinking and related methods
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Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4076930A (en) * 1968-12-13 1978-02-28 James Ellingboe Polysaccharide polyols
US3873514A (en) * 1974-05-17 1975-03-25 Bio Rad Laboratories Preparation of gel for affinity chromatography
US4298500A (en) * 1980-05-05 1981-11-03 Varian Associates, Inc. Mixed phase chromatographic compositions
US4996343A (en) * 1984-05-11 1991-02-26 Northeastern University Stable silica-based ether bonded phases for biopolymer separations
US4705725A (en) * 1986-11-28 1987-11-10 E. I. Du Pont De Nemours And Company Substrates with sterically-protected, stable, covalently-bonded organo-silane films
WO1997023778A1 (en) * 1995-12-21 1997-07-03 Daicel Chemical Industries, Ltd. Packing material for high-speed liquid chromatography
JP4320068B2 (en) * 1997-10-03 2009-08-26 ダイセル化学工業株式会社 Separating agent for optical isomers and process for producing the same
US6752922B2 (en) * 2001-04-06 2004-06-22 Fluidigm Corporation Microfluidic chromatography
DE60212619T2 (en) * 2001-04-12 2006-10-05 Daicel Chemical Industries, Ltd., Sakai METHOD OF PREPARING A FILLER FOR SEPARATING AN OPTICAL ISOMER AND USE IN CHROMATOGRAPHY
JP2004051937A (en) 2002-05-31 2004-02-19 Univ Nihon Polymer composite material and method for producing the same
US20040118762A1 (en) 2002-12-18 2004-06-24 Jishou Xu Packing materials for liquid chromatography using chemically modified diamond powders
US20040121070A1 (en) 2002-12-21 2004-06-24 Jishou Xu Connect diamond powders by cycloaddition reactions
US7427361B2 (en) 2003-10-10 2008-09-23 Dupont Air Products Nanomaterials Llc Particulate or particle-bound chelating agents
US7820130B2 (en) 2003-11-26 2010-10-26 William Marsh Rice University Functionalization of nanodiamond powder through fluorination and subsequent derivatization reactions
US7709053B2 (en) 2004-07-29 2010-05-04 Rohm And Haas Electronic Materials Cmp Holdings, Inc. Method of manufacturing of polymer-coated particles for chemical mechanical polishing
US7858186B2 (en) 2004-11-12 2010-12-28 William Marsh Rice University Fluorinated nanodiamond as a precursor for solid substrate surface coating using wet chemistry
US7326837B2 (en) * 2005-01-07 2008-02-05 Academia Sinica Clinical applications of crystalline diamond particles
US9260653B2 (en) * 2005-08-30 2016-02-16 International Technology Center Enhancement of photoluminescence of nanodiamond particles
WO2006113785A2 (en) * 2005-04-18 2006-10-26 Brigham Young University Laser modification and functionalization of substrates
US20090218276A1 (en) 2008-02-29 2009-09-03 Brigham Young University Functionalized diamond particles and methods for preparing the same
WO2010030827A1 (en) * 2008-09-10 2010-03-18 Brigham Young University Modified diamond particle surfaces and method

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