CN117443363A - Application of expanded graphene oxide as stationary phase material - Google Patents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The invention discloses application of expanded graphene oxide as a stationary phase material. The invention provides application of expanded graphene oxide as a stationary phase material, wherein the expanded graphene oxide is not connected to a support material, and the expanded graphene oxide is obtained by performing microwave treatment after a graphene oxide raw material is formed into a film. When the expanded graphene oxide provided by the invention is used as an adsorbent used in solid phase extraction or a filler used in a fixed phase of liquid chromatography, compared with the adsorbent or filler used in the prior art, the expanded graphene oxide has a remarkably higher maximum combination amount and also has a good recovery rate.
Description
Technical Field
The invention belongs to the technical field of graphene, and relates to application of expanded graphene oxide as a stationary phase material.
Background
Graphene (G) is an allotrope of carbon, its name being from "graphite" and "olefins". The structure of graphene is composed of sp 2 A monolayer planar sheet of bonded carbon atoms. Graphene is very light, with a flake weight of only 0.77 milligrams for 1 square meter. Due to the single-layer structure, the specific surface area is large, and the theoretical value is 2630m 2 And/g. Oxidized stoneGraphene Oxide (GO) is produced by oxidizing Graphene under oxidative chemical conditions, and contains epoxide functional groups on the basal plane of the flake and hydroxyl and carboxyl moieties on the edge, so that Graphene Oxide can be dispersed in water, and the structure of Graphene Oxide is shown in fig. 1.
Carbon allotropes such as activated carbon and carbon black have been studied as adsorbents for compounds such as chlorophenols. If adsorption is reversible, the material may be used as a stationary phase for solid phase extraction (Solid Phase Extraction, SPE) or liquid chromatography separation. Attempts have been made to use the large surface area of G/GO to make it a good adsorbent with large binding capacity. The difficulty encountered is that the G/GO is made from a single sheet, so they form a thin film that plugs the frit and prevents the solvent from passing through. Researchers have therefore thought how to couple G/GO to solid support materials, such as silica beads, magnetic Fe 3 O 4 Beads, capillaries, etc. For example, reference 1 discloses a method for producing an in-tube solid-phase microextraction column, which forms a graphene oxide coating layer of a certain thickness on the inner wall of a capillary tube to obtain an in-tube microextraction column. Reference 2 discloses a method of graphene oxide-bonded silica microspheres as a stationary phase, which uses a coupling agent EDC/NHS to coat graphene oxide to silica microspheres, and finally prepares a liquid chromatography packed column of graphene oxide. Citation 3 discloses the application of layer-by-layer assembly of polyelectrolyte and graphene oxide to open-tube capillary electrochromatography, wherein strong cationic polyelectrolyte polydiallyl dimethyl ammonium chloride is introduced into an empty column, a positive charge aggregation layer is formed on the inner wall of a capillary, and then a dispersion liquid of graphene oxide is introduced.
However, there is still a need to develop stationary phase materials that have greater binding capacity, simpler preparation methods, and are suitable for different types of extraction columns or chromatographic columns.
Citation document
Citation 1: CN103638693A
Citation 2: zhang, xiaoqiong et al, "Preparation and retention mechanism study of graphene and graphene oxide bonded silica microspheres as stationary phases for high performance liquid chromatography," Journal of chromatography.A.vol.1307 (2013): 135-43.Doi: 10.1016/j.chromatography.2013.07.106
Citation 3: qu, qiasu et al, "Layer-by-Layer assembly of polyelectrolyte and graphene oxide for open-tubular capillary electrochromic graphics," Journal of chromatography, A vol.1282 (2013): 95-101.Doi:10.1016/j.chroma.2013.01.055
Disclosure of Invention
Problems to be solved by the invention
Because of the structure limitation of G/GO, when the G/GO is used as an adsorbent for solid phase extraction or liquid chromatography, the fusion cake is easy to block, so that a solvent cannot pass through. The prior art has attempted different methods to achieve G/GO as adsorbent. For example, in references 1 to 2, schemes for coupling G/GO with different solid support materials have been attempted, but these schemes have drawbacks of cumbersome steps and time consumption. Reference 3 will use an electrostatic attraction solution to fix GO to capillary, however, this solution has a lot of material limitations and cannot be widely applied to different types of extraction columns or chromatographic columns. In addition, the above schemes also need to use solid supporting materials, which reduces the content of G/GO in unit volume to a certain extent, thereby affecting the binding capacity and the binding capacity of G/GO, or being limited to micro-extraction, micro-chromatography and the like by adopting capillaries.
In order to solve the above-mentioned problems in the prior art, the inventors used expanded graphene oxide as a stationary phase material, i.e., adsorbent or filler, used in an extraction column or a chromatography column, and creatively found that the porous structure of IGO allows a solvent to pass through without further coupling to a support material, thereby achieving the function as an adsorbent or filler used in an extraction column or a chromatography column. The subsequent examples also demonstrate that the IGO has a greater binding capacity and amount compared to the prior art solutions. For example, the IGO does not require a solid support material compared to silica bound G/GO, so that there is no weight of, for example, silica beads, and thus the amount of adsorbent/filler per unit volume can be increased.
In the present invention, the inventors used IGO as a reversed phase/cation exchange stationary phase material for extraction of small molecules (4-chlorophenol and crystal violet) and peptides (bovine serum albumin trypsin digestion of mixed peptides). The results show that IGO has excellent binding capacity and recovery rate as a solid phase extraction material. Thus, the present invention has been completed.
Solution for solving the problem
Through long-term researches of the inventor, the technical problems can be solved through implementation of the following technical scheme:
[1] the application of the expanded graphene oxide as a stationary phase material.
[2] The use according to [1], wherein the expanded graphene oxide is not attached to a support material.
[3] The use according to [1] or [2], wherein the expanded graphene oxide is obtained by forming a film of a graphene oxide raw material and then performing microwave treatment.
[4]According to [1]]Or [2]]The application, wherein the oxygen ratio of the expanded graphene oxide is 5-15%, and/or the specific surface area of the expanded graphene oxide is 150m 2 And/g.
[5] The use according to any one of [1] to [4], wherein the expanded graphene oxide is prepared by a method comprising the steps of:
a step of forming a graphene oxide film, in which a dispersion liquid containing graphene oxide is treated to obtain a graphene oxide film;
and carrying out microwave treatment on the graphene oxide film obtained in the step of forming the graphene oxide film under the protection of protective gas.
[6] The use according to [5], wherein the power of the microwave treatment is 100W to 800W.
[7] The use according to [5] or [6], wherein the temperature is controlled to 130℃to 200℃during the microwave treatment.
[8] The use according to any one of [5] to [7], wherein the time of the microwave treatment is 10 minutes or less.
[9] The use according to any one of [1] to [8], wherein the stationary phase material is a stationary phase material for solid phase extraction or liquid chromatography.
[10] The use according to [9], wherein the solid phase extraction is selected from the group consisting of reversed phase solid phase extraction, ion exchange solid phase extraction, or reversed phase/ion exchange hybrid solid phase extraction.
[11] The use according to [9], wherein the liquid chromatography is selected from reverse phase chromatography or ion exchange chromatography.
[12] A solid phase extraction or liquid chromatography process wherein the stationary phase material comprises expanded graphene oxide.
ADVANTAGEOUS EFFECTS OF INVENTION
In some embodiments, the expanded graphene oxide provided by the invention can be used as an adsorbent used in solid phase extraction or a filler used in a fixed phase of liquid chromatography, so that different types of extraction columns or chromatographic columns can be used.
In some embodiments, the expanded graphene oxide provided by the invention has a significantly higher maximum binding capacity and good recovery rate compared with the adsorbent or filler used in the prior art when used as an adsorbent used in solid phase extraction or filler used in the stationary phase of liquid chromatography.
Drawings
Fig. 1 is a schematic diagram of a graphene oxide structure.
Fig. 2 is a scanning electron microscope (scanning electron microscope, SEM) image of expanded graphene oxide.
FIG. 3 shows the IGO column and centrifuge tube fittings of different sizes, 20. Mu.l of the microchromatography column in a 1.5ml centrifuge tube, 200. Mu.l of the microchromatography column in a 1.5ml centrifuge tube, and 20. Mu.l of the microchromatography column in a left to right order.
FIG. 4 is a total ion chromatogram of LC/MS of BSA peptide prior to (upper) and after (lower) solid phase extraction with IGO as packing, showing the abundance (y-axis) of ionic peptide eluted from the C18 column at different times (x-axis). The comparative graph shows overall good recovery of the mixed peptide fragments.
FIGS. 5A and 5B are schematic illustrations of calculation of maximum binding of 4-chlorophenol to IGO. Among them, FIG. 5A shows adsorption isotherms of 4-chlorophenol on IGO. Ce is the concentration of 4-chlorophenol at equilibrium. Qe is the adsorption amount of the adsorbent in the equilibrium state per unit mass; fig. 5B is a linearized langmuir diagram for calculating the maximum adsorption amount. The Langmuir adsorption model equation is Qe/qm= bCe/(1+bce). The linearization equation is Ce/qe= (1/Qm) ce+1/(qm×b). Qm represents the maximum adsorption amount.
Detailed Description
Various exemplary embodiments, features and aspects of the invention are described in detail below. The word "exemplary" is used herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
Furthermore, in the following detailed description, numerous specific details are set forth in order to provide a better illustration of the invention. It will be understood by those skilled in the art that the present invention may be practiced without some of these specific details. In other instances, well known methods, procedures, means, equipment and steps have not been described in detail so as not to obscure the present invention.
Unless otherwise indicated, all units used in this specification are units of international standard, and numerical values, ranges of values, etc. appearing in the present invention are understood to include systematic errors unavoidable in industrial production.
In the present specification, the meaning of "can" includes both the meaning of performing a certain process and the meaning of not performing a certain process.
Reference throughout this specification to "some specific/preferred embodiments," "other specific/preferred embodiments," "an embodiment," and so forth, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the elements may be combined in any suitable manner in the various embodiments.
In the present specification, the numerical range indicated by the term "numerical value a to numerical value B" means a range including the end point numerical value A, B.
In the present specification, when "normal temperature" or "room temperature" is used, the temperature may be 10 to 40 ℃.
In this specification, "adsorbent" refers to the packing in a solid phase extraction column that is capable of selectively extracting certain compounds from a sample solution.
In this specification, "Capacity" or "maximum binding Capacity" refers to the total mass of a mass of an adsorbent that is capable of retaining the total mass of a compound (including a target compound and a portion of an interfering substance) under specific conditions.
In the present specification, the specific surface area means the total area of the material per unit mass. The units are m 2 /g, which generally refers to the specific surface area of a solid material, such as a powder, fiber, particle, flake, block, etc., material.
In the present invention, the oxygen ratio refers to the concentration of oxygen atoms in the expanded graphene oxide, and the detection and calculation methods thereof are described in Liang Q, hsie SA, wong CP.Low-temperature solid-state microwave reduction of graphene oxide for transparent electrically conductive coatings on flexible Polydimethylsiloxane (PDMS), chemphyschem.2012;13 (16) 3700-3706.
< application of expanded graphene oxide >
In some aspects of the invention, there is provided the use of expanded graphene oxide as a stationary phase material for solid phase extraction or liquid chromatography.
In some embodiments, the expanded graphene oxide is not attached to a support material. In particular, the expanded graphene oxide is illustratively not coupled to a support material by a coupling agent, or is not attached to a support material by electrostatic attraction, or is attached to, for example, a capillary or other type of extraction column, chromatography column. Support material commonly used in the artSilica beads, magnetic Fe 3 O 4 Beads, capillaries, etc. Thus, in some embodiments, the expanded graphene oxide may be used alone as the stationary phase material.
In some embodiments, the stationary phase material may be an adsorbent used in solid phase extraction or may be a packing used in the stationary phase of liquid chromatography.
The present inventors have found that the porous structure of the IGO allows the solvent to pass through, without further coupling to the support material, to achieve the function as an adsorbent or packing for use in an extraction or chromatography column, and has a higher maximum binding capacity and a wider applicability than G/GO coupled to the support material.
(expanded graphene oxide)
In the present invention, the expanded graphene oxide (Inflated Graphene Oxide, IGO) refers to a porous solid material (see fig. 2) formed by expanding dried GO in a microwave oven. Unlike GO, IGO is insoluble in any solvent and part of the oxygen functionality is reduced due to the high temperature.
(preparation method of expanded graphene oxide)
In some embodiments, the expanded graphene oxide of the present invention is obtained by forming a film of a graphene oxide raw material and then subjecting the film to a microwave treatment.
In some specific embodiments, the expanded graphene oxide of the present invention is prepared by the following method:
a step of forming a graphene oxide film, in which a dispersion liquid containing graphene oxide is treated to obtain a graphene oxide film;
and carrying out microwave treatment on the graphene oxide film under the protection of protective gas.
Graphene oxide raw material
In the present invention, the source of the graphene oxide raw material is not particularly limited, and for example, a commercially available graphene oxide powder may be used. In other embodiments, graphene oxide may also be prepared from a graphite raw material by methods known in the art for preparing graphene oxide, and exemplary methods for preparing graphene oxide currently use more oxidation methods, such as the Brodie method, the Hofmann method, the Hummer method, and the staudenmailer method.
In some specific embodiments, the graphene oxide is prepared using the Hummer method, for example, using the literature Hummers WS, offeman re.preparation of graphic oxides j American Chem Soc 1958;80 1339. The method described in (6).
In some specific embodiments, the number ratio of C atoms to O atoms in the graphene oxide is about 1: (1 to 3), preferably 1: (1-2), e.g., 1:1.2, 1:1.4, 1:1.6, or 1:1.8.
In some specific embodiments, the graphene oxide has a specific surface area of about 0.5 to 2m 2 Preferably 0.7 to 1m 2 /g, e.g. 0.7m 2 /g、0.8m 2 /g、0.85m 2 /g or 0.9m 2 And/g. The specific surface area of the expanded graphene oxide can be 150m after the expanded graphene oxide is obtained through the steps of forming the graphene oxide film and treating the graphene oxide film by microwaves in the preparation method of the expanded graphene oxide within the specific surface area range 2 And/g.
Regarding the purity of the graphene oxide raw material, the present invention recognizes that the improvement of the purity of the graphene oxide raw material is advantageous for the overall performance of the final solid phase extraction or liquid chromatography, such as the binding capacity or the binding amount, and in some specific embodiments, graphene oxide having a purity of 95% or more, preferably 98% or more, may be used.
For the above graphene oxide raw material, pretreatment may be performed before the film formation of the graphene oxide described below is performed to further improve the purity.
The pretreatment means is not particularly limited, and may include a washing step or the like in some specific embodiments of the present invention. There is no particular limitation in the washing step, and preferably, reference is made to Kim F, luo J, cruz-Silva R, cote LJ, sohn K, huang J.Self-Propagating Domino-like Reactions in Oxidized Graphite.advanced Functional materials.2010;20 (17) 2867-73. Two-step acid-acetone washes were used.
Graphene oxide film formation
In the present invention, the graphene oxide raw material is prepared as a dispersion liquid having a certain solid content, and the dispersion liquid containing graphene oxide is subjected to a film forming treatment to obtain a graphene oxide thin film.
In some embodiments, the graphene oxide feedstock is formulated as a dispersion of a certain solids content. For the solid content of the graphene oxide-containing dispersion liquid, the solid content may be 0.5 to 30mg/mL, preferably 1 to 10mg/mL, more preferably 2 to 4mg/mL, for example 2mg/mL, 3mg/mL or 4mg/mL in the present invention.
As the film forming means which can be used in the present invention, there may be mentioned knife coating, casting, spraying, spin coating and vacuum filtration to form a film.
In some processes for obtaining the graphene oxide film, a drying treatment step may be employed. Examples of the drying method include oven heating drying and room temperature drying; more preferably, the film-forming of graphene oxide is dried at room temperature. The resulting graphene oxide film may be subjected to any washing treatment.
In some embodiments, film formation and drying are alternately repeated to achieve a desired thickness of graphene oxide film, e.g., 15 or more layers of graphene oxide. In other embodiments, a dispersion of graphene oxide-containing feedstock may also be placed in an open container until it dries to form a film of graphene oxide (which may also be referred to as a cake of graphene oxide).
Microwave treatment of graphene oxide films
In the invention, the step of microwave treatment of the graphene oxide film comprises the step of carrying out microwave treatment on the graphene oxide film under the protection of protective gas.
In the present invention, the apparatus for performing the microwave treatment is not particularly limited, and may be, for example, a commercially available variable frequency microwave system (VFM, microcoure 2100,Lambda Technologies) equipped with a shielding gas shield (for example, equipped with a nitrogen shield).
In some specific embodiments, the microwave treatment is at a power of 100W to 800W, preferably 300W to 600W, such as 300W, 400W, 500W or 600W.
In some specific embodiments, the temperature is controlled during the microwave treatment at 130 ℃ to 200 ℃, preferably 150 ℃ to 180 ℃.
In some specific embodiments, the microwave treatment time is less than 10 minutes, preferably between 8 and 10 minutes, such as 8 minutes and 9 minutes.
In some specific embodiments, the microwave treatment has a frequency of 1GHz to 10GHz, preferably 3GHz to 8GHz, and more preferably 5GHz to 7GHz.
In some specific embodiments, the microwave treatment has a frequency bandwidth of 0.5GHz to 3GHz, preferably 1GHz to 3GHz, and more preferably 1GHz to 2GHz.
In some specific embodiments, the microwave treatment is scanned at a rate of from 0.01 seconds to 1 second, preferably from 0.05 seconds to 0.5 seconds, more preferably from 0.05 seconds to 0.3 seconds.
In the present invention, the graphene oxide film after the above-described microwave treatment forms expanded graphene oxide in which the oxygen ratio is 5 to 15%, preferably 8 to 12%, for example 8%, 9%, 10%, 11% or 12% (illustratively, the oxygen ratio is detected by X-ray photoelectron spectroscopy (X-ray photoelectron spectroscopy, XPS)).
The specific surface area of the expanded graphene oxide is 150m 2 Above/g, preferably 160m 2 Over/g, 170m 2 Over/g, 190m 2 Over/g, 230m 2 Over/g, 260m 2 /g or more or 290m 2 And/g. In some embodiments, the expanded graphene oxide has a specific surface area of 150 to 300m 2 And/g. In the invention, the specific surface area of the expanded graphene oxide is represented by N 2 BET specific surface area detection. Compared to a higher or lower oxygen ratio and specific surface area at which expanded graphene oxide is used as an adsorbent in solid phase extraction, or immobilization by liquid chromatographyThe filler used in the phase has a significantly higher maximum bound content and also has good recovery.
In some embodiments, N 2 BET specific surface area assay 77K N can be recorded using an Auto-sorb-1 instrument from Quantachrome, inc 2 Adsorption isotherms. If the BET correlation is good, according to N 2 The BET surface area is calculated over a range of adsorption isotherm relative pressures from 0.05 to 0.30. When the linear correlation factor is at least R 2 When=0.9999, all BET specific surface area values were recorded.
In the present invention, the expanded graphene oxide prepared by the above-described method may be used as a stationary phase material for solid phase extraction or liquid chromatography (preferably as a single material), for example, an adsorbent used in solid phase extraction, or a filler used in a stationary phase of liquid chromatography.
(solid phase extraction)
In the present specification, "solid phase extraction (Solid Phase Extraction, abbreviated as SPE)", also called solid phase extraction, is a separation technique that combines processes such as selective retention and selective elution. When complex sample solution passes through the adsorbent (Sorbent), the adsorbent selectively retains the target substance (Aimed Compound) and a small amount of components similar to the target substance in property by polar interaction, hydrophobic interaction or ion exchange, and other components flow out of the column through the adsorbent, and then the target substance is selectively eluted by another solvent system, so that separation, purification and enrichment of complex samples are realized.
Solid phase extraction is mainly divided into normal phase, reverse phase, ion exchange and mixed solid phase extraction according to the difference of the adsorbent filler and the adsorption mechanism.
In the present specification, "reversed phase solid phase extraction" is to separate organic solutes from polar phases (water) by using nonpolar adsorbents (carbohydrates or polymers) on stationary phases, and the forces of action between nonpolar substances are van der Waals attractive forces, and the affinity of the adsorbents to the solutes is mainly due to the hydrophobicity thereof.
In the present specification, "ion-exchange solid phase extraction" is to achieve separation by high-energy interaction between ions.
In some embodiments of the invention, the solid phase extraction is selected from reverse phase solid phase extraction, ion exchange solid phase extraction, or reverse phase/ion exchange hybrid solid phase extraction. That is, the expanded graphene oxide provided by the invention can be used as (preferably independently used as) an adsorbent in reversed phase solid phase extraction, an adsorbent in ion exchange solid phase extraction, or an adsorbent in reversed phase/ion exchange mixed solid phase extraction. And as demonstrated in the examples below, the expanded graphene oxide has a higher maximum binding capacity in the solid phase extraction described above than the conventional reversed phase material C18, and the adsorption material carbon black and G covalently bound silica beads commonly used in the prior art.
(liquid chromatography)
In this specification, "chromatography" refers to a technique that uses components that interact differently between two phases, where the "mobile phase" is the fluid that carries the sample through the entire system and the "stationary phase" is the stationary phase, i.e., the chromatographic column. The main purpose of chromatography is to separate and quantify the targets in the mixture. Chromatography is classified into gas chromatography and liquid chromatography according to the states of mobile phase and stationary phase. According to the separation principle, chromatography is divided into: adsorption chromatography, partition chromatography, ion exchange chromatography, and size exclusion chromatography. Wherein the partition chromatography includes forward chromatography and reverse chromatography.
In the present specification, "liquid chromatography" is a chromatographic separation method using a liquid as a mobile phase.
In the present specification, "reversed phase chromatography" refers to chromatography in which the polarity of the mobile phase is greater than that of the stationary phase.
In some embodiments of the invention, the liquid chromatography is selected from reverse phase chromatography or ion exchange chromatography. That is, the expanded graphene oxide provided by the present invention may be used as (preferably alone as) a filler in a stationary phase in reverse phase chromatography or ion exchange chromatography.
< stationary phase Material and method of treatment >
In some aspects of the invention, a stationary phase material for solid phase extraction or liquid chromatography is provided, the stationary phase material comprising expanded graphene oxide.
In some aspects of the invention, a solid phase extraction or liquid chromatography process is provided in which the stationary phase material comprises expanded graphene oxide.
In some embodiments, the expanded graphene oxide is prepared by the method described in "method of preparing expanded graphene oxide" above.
In some preferred embodiments, the expanded graphene oxide is not attached to a support material.
In some preferred embodiments, the stationary phase material consists of expanded graphene oxide.
Examples
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Experimental method
1. IGO production
GO is obtained by preparation using the Hummer method (cf. Hummers WS, offeman RE. Preparation of graphic oxides. J American Chem Soc 1958;80 (6): 1339.) and further purified by two-step acid-acetone washes (cf. Kim F, luo J, cruz-Silva R, cote LJ, sohn K, huang J. Self-Propagating Domino-like Reactions in Oxidized graphic. Advanced Functional materials.2010;20 (17): 2867-73.).
The obtained GO is detected, the number ratio of C atoms to O atoms in the GO is 1:1.8, and the specific surface area is about 0.85m 2 /g。
The GO multilayer film was prepared by pipetting 2mg/ml of GO solution onto clean polystyrene substrate and drying overnight at room temperature. The thickness of the existing GO membrane was increased daily by pipetting fresh 2mg/ml GO solution onto the previously dried membrane until the desired thickness was reached. Drying is completedAfter that, the GO film was peeled off from the polystyrene surface. A variable frequency microwave system (VFM, microcure 2100,Lambda Technologies) with nitrogen protection was provided, with a frequency of 6.425GHz, a bandwidth of 1.15GHz, and a scan rate of 0.1 seconds. The power of the microwave oven is controlled at 500w, and the temperature is controlled at 170 ℃ through an infrared wave temperature sensor for 8 minutes. Finally, the surface morphology of the IGO sample was characterized using a scanning electron microscope (scanning electron microscope, SEM). The oxygen ratio of the expanded graphene oxide is 10% by adopting X-ray photoelectron spectroscopy detection, and N is adopted 2 BET detection of the specific surface area of the expanded graphene oxide was 171m 2 /g。
2. Solid phase extraction molecular recovery determination
2.1, 4-chlorophenol
4-chlorophenol was dissolved in 0.1% aqueous acetic acid to 0.05mg/ml. 1ml of the sample was passed through a small column containing 5mg of IGO and eluted with 1ml of methanol (0.1% ammonia). The sample and the eluent were analyzed by HPLC, and the recovery rate was calculated by comparing the peak area of the eluent with the peak area of the sample.
2.2 crystal violet
Crystal violet was dissolved in water to 0.05mg/ml. A0.1 ml sample was taken through a small column containing 0.5mg IGO and eluted with 1ml of 1% trifluoroacetic acid in acidified methanol. The eluate was concentrated by vacuum centrifugation and redissolved in 0.1ml of water. The sample and the eluent were analyzed by HPLC to calculate the recovery rate.
2.3 peptide fragments
Trypsin digestion of Bovine Serum Albumin (BSA) peptide (New England Biolabs, 50-445-0) was brought to a concentration of 1mg/ml with 0.5% formic acid. 20 μl of the sample was passed through a small column containing 0.5mg IGO. Elution was performed with 1ml of methanol containing 1% trifluoroacetic acid. The eluate was concentrated by vacuum centrifugation and redissolved in 20 μl 0.5% formic acid. Samples were analyzed by LC-MS before and after extraction. Recovery was calculated for the peak area of the first isotope peak extracted for the selected ion.
2.4、HPLC
Shimadzu high performance liquid chromatography HPLC equipped with Agilent Zorbax C18 column (3.5 μm,2.1×50 mm). Solvent a and solvent B were 0.1% formic acid water and 0.1% acetonitrile formate, respectively. The detection wavelengths of the 4-chlorophenol and the crystal violet are 282nm and 583nm respectively. Flow rate 0.2ml/min, gradient: 0-1min 30% B,1-6min 70% B,6-7min 100% B.
2.5、LC/MS
Agilent 1260HPLC was used in combination with Agilent 6530QTOF mass spectrometry, equipped with Agilent Zorbax C18 column (3.5 μm,2.1 x 50 mm). Solvent A was 0.1% formic acid water and solvent B was 0.1% acetonitrile formate. Gradient from 5% B to 65% B, flow rate of 0.25ml/min, run for 10min. The ions are scanned over a mass range of 100-3000 Da.
3. Binding Capacity assay
4-chlorophenol was dissolved in 0.1% acetic acid to give different initial concentrations. Different concentrations of 0.5ml 4-chlorophenol were mixed with 0.5mg IGO or 50mg C18 beads (55-105 μm, voltch) in 1.5ml centrifuge tubes at room temperature for 2.5 hours. Wherein the concentration of IGO repeat 1 is 0.5, 0.4, 0.3, 0.25, 0.2, 0.15, 0.1, 0.05mg/ml; the concentration of IGO repetition 2 is 0.5, 0.4, 0.2, 0.05mg/ml; the concentration of C18 beads was 0.05, 0.04, 0.02, 0.005mg/ml. 10. Mu.l of each sample was taken before and after IGO adsorption, and the adsorption amount was measured by HPLC. The maximum binding was calculated using a linearized Langmuir plot.
Test results
The SPE cartridge was made by loading IGO directly into a small cartridge, which in turn was loaded into a 1.5ml centrifuge tube, and sample loading and elution was performed by centrifugation (FIG. 3).
Test result 1, IGO solid-phase extraction recovery result
1.1 Small molecules
The results for 4-chlorophenol (mw=128.6) are shown in formula I below, with the recovery of the IGO solid phase extraction of 4-chlorophenol: 94.5±0.2% (n=2).
The result of crystal violet (mw= 373.5) is shown in formula II below, and the recovery rate of the solid phase extraction of IGO of crystal violet is: 97.3±0.6% (n=2).
The above results show that IGO as a filler has good recovery of both 4-chlorophenol (neutral molecules at 0.1% acetic acid) and basic molecular crystal violet (positively charged at 1% trifluoroacetic acid). IGO is an excellent solid phase extraction material that can be used to concentrate target compounds and/or remove impurities from the original sample.
1.2 Mixed peptides
The sample for this test is a mixture of Bovine Serum Albumin (BSA) peptides digested by trypsin. Trypsin is a protease that cleaves the amino acids lysine and arginine. The results indicate that the polypeptides have good recovery over a broad isoelectric point and hydrophobicity (indicated by retention time of the C18 column) (see fig. 4, and table 1 below). The above results indicate that IGO can be applied in proteomics.
Table 1. Recovery of BSA peptide fragments of different hydrophobicity (C18 retention time) and isoelectric point (n=2).
| Peptides | SEQ ID NO: | Retention (minutes) | Isoelectric point | Recovery rate |
| AEFVEVTK | 1 | 3.6 | 4.5 | 94.2±2.3％ |
| LVVSTQTALA | 2 | 4.2 | 5.5 | 71.2±5.9％ |
| YLYEIAR | 3 | 4.2 | 6.0 | 98.6±1.4％ |
| LVNELTEFAK | 4 | 4.8 | 4.5 | 96.7±3.3％ |
| HLVDEPQNLIK | 5 | 4.1 | 5.3 | 96.7±3.3％ |
| TVMENFVAFVDK | 6 | 6.0 | 4.4 | 70.4±7.6％ |
| GSFLYEYSR | 7 | 3.8 | 6.0 | 92.9±0.5％ |
| DDPHACYSTVFDK | 8 | 4.1 | 4.4 | 68.3±1.4％ |
| FKDLGEEHFK | 9 | 3.7 | 5.5 | 73.1±0.4％ |
| LFTFHADICTLPDTEK | 10 | 5.3 | 4.5 | 100.0±0.0％ |
| RHPEYAVSVLLR | 11 | 4.6 | 8.8 | 72.7±1.5％ |
| DLGEEHFK | 12 | 3.3 | 4.7 | 77.2±0.0％ |
| YICDNQDTISSK | 13 | 3.2 | 4.2 | 89.9±4.0％ |
Test result 2, maximum binding force as reverse phase material
The maximum binding of 4-chlorophenol to IGO at room temperature was 176.2 ±19.9mg/g (n=2) (see fig. 5A-5B), whereas the maximum binding to conventional reversed phase material C18 was only 60.2 μg/g. It has been reported that the maximum binding capacity of carbon black, a common adsorbent material, is 10-25mg/G at 25℃and that of G covalently bound silica beads is 156.8. Mu.g/G [1,2] 。
Reference to the literature
1.Shih,Y.H.,et al.,Distinctive sorption mechanisms of 4-chlorophenol with black carbons as elucidated by different pH.Science of the Total Environment,2012.433:p.523-529.
2.Liu,Q.,et al.,Graphene and Graphene Oxide Sheets Supported on Silica as Versatile and High-Performance Adsorbents for Solid-Phase Extraction.Angewandte Chemie-International Edition,2011.50(26):p.5913-5917.
The test results show that IGO has very high binding capacity as a reversed phase material, reaching mg/g level, whereas conventional head-assisted adsorbents are only μg/g level.
In conclusion, the expanded graphene oxide IGO can be used as an excellent high-capacity reversed-phase and ion exchange mixed mode solid-phase extraction material. It can be used not only for solid phase extraction but also for molecular separation in liquid chromatography, since it has the potential to more widely separate compounds based on different mechanisms (hydrophobicity and charge).
It should be noted that, although the technical solution of the present invention is described in specific examples, those skilled in the art can understand that the present invention should not be limited thereto.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described. The terminology used herein was chosen in order to best explain the principles of the embodiments, the practical application, or the technical improvements in the marketplace, or to enable others of ordinary skill in the art to understand the embodiments disclosed herein.
Claims (12)
1. The application of the expanded graphene oxide as a stationary phase material.
2. The use of claim 1, wherein the expanded graphene oxide is not attached to a support material.
3. The use according to claim 1 or 2, wherein the expanded graphene oxide is obtained by forming a film of a graphene oxide raw material and then subjecting the film to a microwave treatment.
4. The use according to claim 1 or 2, wherein the expanded graphene oxide has an oxygen ratio of 5-15%; and/or the specific surface area of the expanded graphene oxide is 150m 2 And/g.
5. The use according to any one of claims 1 to 4, wherein the expanded graphene oxide is prepared by a process comprising the steps of:
a step of forming a graphene oxide film, in which a dispersion liquid containing graphene oxide is treated to obtain a graphene oxide film;
and carrying out microwave treatment on the graphene oxide film obtained in the step of forming the graphene oxide film under the protection of protective gas.
6. The use according to claim 5, wherein the microwave treatment has a power of 100W to 800W.
7. Use according to claim 5 or 6, wherein the temperature is controlled between 130 ℃ and 200 ℃ during the microwave treatment.
8. Use according to any one of claims 5 to 7, wherein the microwave treatment is for a period of time of 10 minutes or less.
9. The use according to any one of claims 1 to 8, wherein the stationary phase material is a stationary phase material for solid phase extraction or liquid chromatography.
10. The use according to claim 9, wherein the solid phase extraction is selected from reverse phase solid phase extraction, ion exchange solid phase extraction, or reverse phase/ion exchange hybrid solid phase extraction.
11. Use according to claim 9, wherein the liquid chromatography is selected from reverse phase chromatography or ion exchange chromatography.
12. A solid phase extraction or liquid chromatography process wherein the stationary phase material comprises expanded graphene oxide.
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