CN111774043B - Chromatographic packing of poly (N-isopropylacrylamide) -modified graphene quantum dots and preparation method and application thereof - Google Patents
Chromatographic packing of poly (N-isopropylacrylamide) -modified graphene quantum dots and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a chromatographic packing of poly (N-isopropylacrylamide) -modified graphene quantum dots, and a preparation method and application thereof, and belongs to the technical field of high performance liquid chromatography materials. According to the preparation method, functional groups of GQDs and PNIPAAm can be bonded on the surface of the porous silicon ball to obtain the chromatographic packing of the poly (N-isopropylacrylamide) -modified graphene quantum dots, belonging to a mixed-mode high performance liquid chromatography packing, and having excellent physical structures such as high mechanical strength, good physical and chemical properties and the like of the silica gel packing; the method also has the advantages of high separation speed, high separation selectivity and the like, can make up the defects of single-mode chromatography in complex sample analysis, and improves the separation efficiency.
Description
Technical Field
The invention belongs to the technical field of high performance liquid chromatography materials, and particularly relates to a chromatographic packing of a poly (N-isopropylacrylamide) -modified graphene quantum dot, and a preparation method and application thereof.
Background
The chromatographic stationary phase is the most core part of a high performance liquid chromatography system, and in order to meet the requirements of high selectivity and high sensitivity when complex samples are analyzed, the development of a novel chromatographic stationary phase with high separation efficiency and good selectivity has become a hotspot of research in the separation science field.
The mixed-mode chromatographic stationary phase has a plurality of functional group ligands, is a powerful tool for separating and analyzing a plurality of compounds, can provide a plurality of acting forces for the retention of solute molecules in separation and analysis, can be separated according to different characteristics of analysis substances, improves the separation selectivity, and is suitable for the separation and analysis of complex samples. At present, a traditional Chinese medicine complex system contains a plurality of hydrophilic chemical components with pharmacological activity, wherein nucleoside components play important roles in the aspects of immunoregulation, cardiovascular diseases, tumor resistance and the like, but the liquid chromatography separation analysis of the strongly hydrophilic mixture is a technical problem in analysis and test. Although the existing methods such as Gas Chromatography (GC), mass Spectrometry (MS), gas chromatography-mass spectrometry (GC/MS), capillary Electrophoresis (CE), high Performance Liquid Chromatography (HPLC) and the like can realize the analysis of hydrophilic substances such as nucleosides, the analysis conditions are relatively complex, so that the method has important significance for establishing a method for realizing the rapid separation of the hydrophilic substances such as nucleosides in an actual system.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a chromatographic packing of graphene quantum dots modified by poly (N-isopropylacrylamide); the invention also aims to provide a preparation method of the chromatographic packing of the poly (N-isopropylacrylamide) -modified graphene quantum dot; the invention also aims to provide application of the chromatographic packing of the poly (N-isopropylacrylamide) -modified graphene quantum dots in a high performance liquid chromatography column.
In order to achieve the purpose, the invention provides the following technical scheme:
1. a chromatographic filler of poly (N-isopropylacrylamide) -modified graphene quantum dots, comprising silicon spheres and graphene quantum dots and poly (N-isopropylacrylamide) bonded to the surfaces of the silicon spheres.
2. The preparation method of the chromatographic packing comprises the following steps:
(1) Bonding graphene quantum dots on the surface of the silicon sphere: carrying out amidation reaction on the graphene quantum dots on the surfaces of the silicon spheres bonded with the silanization reagent to generate an amide bonding material, namely the silicon spheres bonded with the graphene quantum dots;
(2) Continuously bonding a RAFT transfer reagent on the surface of the silicon ball bonded with the graphene quantum dot: carrying out esterification reaction on the RAFT transfer reagent on the surface of the silicon ball bonded with the graphene quantum dot in the step (1) to obtain the silicon ball bonded with the graphene quantum dot and the RAFT transfer reagent;
(3) Bonding poly (N-isopropylacrylamide) on the silicon spheres of the bonded graphene quantum dots and RAFT transfer reagent: and (3) carrying out reversible addition-fragmentation chain transfer polymerization reaction on the surface of the silicon ball bonded with the graphene quantum dot and the RAFT transfer reagent in the step (3) by using N-isopropylacrylamide, thus obtaining the chromatographic packing of the poly (N-isopropylacrylamide) -modified graphene quantum dot.
Preferably, the silicon spheres bonded with the silanization reagent in the step (1) are prepared according to the following method:
a. activating the porous silicon spheres by acid to obtain activated silicon spheres;
b. and performing amination treatment on the surface of the activated silicon sphere by using a silylation reagent to obtain the silanization reagent-bonded silicon sphere.
Preferably, the porous silicon spheres have a particle diameter of 2 to 10 μm and a pore diameter of
The silanization reagent is 3-aminopropyl triethoxysilane.
Preferably, the preparation method of the silicon ball bonded with the silylation reagent comprises the following specific steps:
a. the particle diameter is 2 to 10 mu m and the aperture is
The porous silicon balls are evenly dispersed by 0.1 to 5mol/L HCl through ultrasound, stirred and reacted for 1 to 24 hours at the temperature of between 50 and 110 ℃, filtered, washed to be neutral by water, and dried at the temperature of 150 ℃ to obtain activated silicon balls;
b. firstly dispersing the activated silicon spheres in dry toluene, adding 3-aminopropyltriethoxysilane to react for 3-24 h at 20-110 ℃ under the protection of nitrogen, then sequentially performing suction filtration and cleaning by using toluene, pure water and methanol, and finally performing vacuum drying at normal temperature for 5-24 h or at 50-100 ℃ for 2-10 h to obtain the silicon spheres bonded with the silanization reagent.
Preferably, the mass-to-volume ratio of the activated silicon spheres to the 3-aminopropyltriethoxysilane is 5.
Preferably, the step (1) of bonding the graphene quantum dots on the surface of the silicon spheres comprises the following specific steps:
a. preparing a dispersion solution from graphene oxide quantum dots with the particle size of 1-100 nm and water according to the mass-to-volume ratio of 1-3;
b. adding the silicon spheres bonded with the silylation reagent into the mixed solution according to the volume mass ratio of 5-25 g to 1,mL, and carrying out an amide reaction at 25-50 ℃ for 2-24 h;
c. and filtering after the reaction is finished, washing the reaction product by using water and methanol in sequence, and drying the reaction product for 5 to 24 hours at normal temperature in vacuum or 2 to 10 hours at the temperature of between 50 and 100 ℃ in vacuum to obtain the silicon spheres bonded with the graphene quantum dots.
Preferably, the step (2) of continuously bonding a RAFT transfer reagent to the surface of the silicon spheres bonded with the graphene quantum dots comprises the specific steps of:
a. adding dodecyl trithiocarbonate and 4-Dimethylaminopyridine (DMAP) into a tetrahydrofuran solvent to form a solution containing a chain transfer agent, wherein the volume mass ratio of the tetrahydrofuran solvent to the dodecyl trithiocarbonate to the 4-dimethylaminopyridine is 500-1000, and the volume mass ratio of mL to g is;
b. adding the silicon spheres bonded with the graphene quantum dots into the solution containing the chain transfer agent according to the volume-to-mass ratio of 5-25 g;
c. and filtering after the reaction is finished, washing with dichloromethane, pure water and methanol in sequence, and drying in vacuum for 5-24 h at normal temperature or 2-10 h at 50-100 ℃ to obtain the silicon spheres bonded with the graphene quantum dots and the RAFT transfer reagent.
Preferably, the volume mass ratio of the tetrahydrofuran solvent, the dodecyl trithiocarbonate and the 4-dimethylaminopyridine is 1000.
Preferably, the mass ratio of the silicon spheres bonded with the graphene quantum dots to Dicyclohexylcarbodiimide (DCC) is 25.
Preferably, the step (3) of bonding poly (N-isopropylacrylamide) on the silicon spheres bonded with the graphene quantum dots and the RAFT transfer reagent comprises the specific steps of:
a. adding Azobisisobutyronitrile (AIBN) and N-isopropyl acrylamide into a 1, 4-dioxane solvent according to the volume mass ratio of 10-50;
b. adding the silicon spheres bonded with the graphene quantum dots and the RAFT transfer reagent into the mixed solution according to the volume-mass ratio of 5-25 g to 1,mL, vacuumizing, introducing nitrogen for 30-60min, and reacting for 2-24 h at 25-85 ℃;
c. and after the reaction is finished, filtering, washing with tetrahydrofuran and methanol in sequence, and performing vacuum drying at normal temperature for 5-24 h or at 50-100 ℃ for 2-10 h to obtain the chromatographic packing of the poly (N-isopropylacrylamide) -modified graphene quantum dots, wherein poly (N-isopropylacrylamide) is bonded on silicon spheres bonded with the graphene quantum dots and the RAFT transfer reagent.
Preferably, the volume mass ratio of the 1, 4-dioxane, azobisisobutyronitrile (AIBN) and N-isopropylacrylamide is 10.
3. The chromatographic packing of the poly (N-isopropylacrylamide) -modified graphene quantum dots is applied to a high performance liquid chromatography column.
Preferably, the application is hydrophilic chromatography or reverse phase chromatography.
Preferably, the hydrophilic chromatographic separation specifically comprises: the chromatographic packing of the poly (N-isopropylacrylamide) -modified graphene quantum dots is used as a stationary phase of a high performance liquid chromatography column for rapidly detecting or separating hydrophilic substances.
Preferably, the hydrophilic substance is a nucleoside, a nucleoside base, a water-soluble vitamin or an amino acid.
Preferably, during the hydrophilic chromatographic separation, any one of acetonitrile/water, acetonitrile/formic acid water, acetonitrile/acetic acid water, acetonitrile/ammonium formate water, methanol/formic acid water, methanol/acetic acid water or methanol/ammonium formate water is selected as a mobile phase.
Preferably, the concentration of formic acid or acetic acid is 0.1 to 1.0% and the concentration of ammonium formate is 10 to 100mM.
Preferably, the flow rate of the mobile phase is 0.6 to 1.2mL/min.
Preferably, the detection wavelength under the hydrophilic chromatographic separation is 214nm or 254nm, and the column temperature is 20-50 ℃.
Preferably, the reverse phase chromatographic separation is specifically: the chromatographic packing of the poly (N-isopropylacrylamide) -modified graphene quantum dots is used as a stationary phase of a high performance liquid chromatography column for rapidly detecting or separating benzene, biphenyl, polycyclic aromatic hydrocarbon, aniline or phenol substances containing different numbers of carbon atom alkyl chain substitutions.
Preferably, during the reversed phase chromatographic separation, any one of acetonitrile/water, acetonitrile/formic acid water, acetonitrile/acetic acid water, acetonitrile/ammonium formate water, methanol/formic acid water, methanol/acetic acid water and methanol/ammonium formate water is selected as a mobile phase.
Preferably, the concentration of formic acid or acetic acid is 0.1 to 1.0%, and the concentration of ammonium formate is 10 to 100mM.
Preferably, the flow rate of the mobile phase is 0.6 to 1.2mL/min.
Preferably, the detection wavelength under the reversed phase chromatographic separation is 214nm or 254nm, and the column temperature is 20-50 ℃.
The invention has the beneficial effects that:
1. the invention provides a chromatographic packing of poly (N-isopropylacrylamide) -modified graphene quantum dots, which is characterized in that graphene oxide quantum dots and poly (N-isopropylacrylamide) are bonded on the surface of a silicon ball to form a poly (N-isopropylacrylamide) -modified graphene quantum dot high-performance liquid chromatography packing, belongs to a mixed-mode high-performance liquid chromatography packing, has excellent physical structures such as high mechanical strength, good physical and chemical properties and the like of a silica gel packing, has the advantages of high separation speed, high separation selectivity and the like, can make up the defects of a single-mode chromatogram in complex sample analysis, improves the separation efficiency, and can be applied to reversed-phase or hydrophilic chromatographic separation;
2. the invention provides a preparation method of a chromatographic packing of a poly (N-isopropylacrylamide) -modified graphene quantum dot, which has a simple preparation process and is easy to operate;
3. the high performance liquid chromatography filler prepared by the invention can respectively play a role in reversed phase/hydrophilicity when being used as a fixed phase of high performance liquid chromatography, plays a good role in separating corresponding substances, and can realize the rapid and effective separation of hydrophilic substances such as nucleosides in an actual system.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims thereof.
Drawings
For a better understanding of the objects, aspects and advantages of the present invention, reference will now be made to the following detailed description taken in conjunction with the accompanying drawings in which:
FIG. 1 is an infrared spectrum of each substance in the preparation process, wherein a is Silica; b is Sil-APTES; c is Sil-GQDs; d is Sil-GQDs-DMP; e is Sil-GQDs-PNIPAAm;
FIG. 2 is a thermogravimetric analysis of the various species in the process, wherein a is Silica; b is Sil-APTES; c is Sil-GQDs; d is Sil-GQDs-DMP; e is Sil-GQDs-PNIPAAm;
FIG. 3 shows the delay times of different alkylbenzene compounds in a high performance liquid chromatography column using a chromatographic packing of poly (N-isopropylacrylamide) -modified graphene quantum dots as a stationary phase, wherein 1 is toluene, 2 is ethylbenzene, 3 is N-propylbenzene, 4 is butylbenzene, and 5 is N-pentylbenzene;
fig. 4 shows the delay time of different polycyclic aromatic hydrocarbon compounds in a high performance liquid chromatography column using a chromatographic filler of poly (N-isopropylacrylamide) -modified graphene quantum dots as a stationary phase, wherein 1 is naphthalene, 2 is acenaphthene, 3 is phenanthrene, 4 is pyrene, and 5 is chrysene;
fig. 5 is a graph showing the delay times of different nucleoside compounds in a high performance liquid chromatography column using a chromatographic packing with poly (N-isopropylacrylamide) -modified graphene quantum dots as a stationary phase, wherein 1 is thiourea, 2 is thymidine, 3 is deoxyadenosine, 4 is adenosine, 5 is uridine, 6 is cytidine, and 7 is cytosine;
fig. 6 shows the delay times of different phenol compounds in a high performance liquid chromatography column using a chromatographic filler of a poly (N-isopropylacrylamide) -modified graphene quantum dot as a stationary phase, wherein 1 is hydroquinone, 2 is o-nitrophenol, and 3 is p-nitrophenol;
FIG. 7 shows the delay times of different aniline compounds in a high performance liquid chromatography column using a chromatographic packing of poly (N-isopropylacrylamide) -modified graphene quantum dots as a stationary phase, wherein 1 is p-phenylenediamine, 2 is o-phenylenediamine, 3 is biphenyldiamine, 4 is 1-naphthylamine, 5 is 2, 4-dinitroaniline, and 6 is diphenylamine;
fig. 8 shows that the chromatographic packing of the poly (N-isopropylacrylamide) -modified graphene quantum dots is a stationary phase, and the nucleoside hydrophilic substances in the isatis root particles are separated in a high performance liquid chromatography column, wherein 1 is uridine, 2 is syringin, 3 is adenosine, 4 is adenine, a is the standard retention time of each substance, and b is the retention time of the substance separated from the traditional Chinese medicine isatis root particles.
Detailed Description
The following embodiments of the present invention are provided by way of specific examples, and other advantages and effects of the present invention will be readily apparent to those skilled in the art from the disclosure herein. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It should be noted that, in the following embodiments, features in the embodiments may be combined with each other without conflict.
Example 1
The preparation method of the chromatographic packing of the poly (N-isopropylacrylamide) -modified graphene quantum dots comprises the following steps:
1. preparation of silica spheres bound with silylation agent:
(1) Weighing the particles with the particle diameter of 2-10 mu m and the pore diameter of
Performing ultrasonic reaction on 5g of the porous silicon spheres by using 1mol/L HCl at 90 ℃ for 3 hours to uniformly disperse the porous silicon spheres, filtering the mixture, washing the mixture to be neutral by using purified water, and drying the mixture at 150 ℃ for 24 hours to obtain activated silicon spheres;
(2) Weighing 2.5g of activated silicon spheres, using dry toluene as a solvent, adding 2mL of 3-Aminopropyltriethoxysilane (APTES), uniformly dispersing, stirring and refluxing for 3h at 110 ℃ under the protection of nitrogen, sequentially filtering and washing a product after the reaction is finished by toluene, pure water and methanol, and performing vacuum drying for 24h at 50 ℃ to obtain silicon spheres (Sil-APTES) bonded with a silanization reagent for later use.
2. Preparing silicon spheres bonded with the graphene quantum dots:
(1) Adding 0.3g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS) into 150mL of dispersion liquid formed by graphene oxide quantum dots (with the particle size of 1-100 nm) and water, wherein the concentration of the graphene oxide quantum dots is 2mg/mL, and stirring for reaction for 30min to activate carboxyl to obtain mixed liquid;
(2) Then 2.5g of the prepared silicon spheres (Sil-APTES) bonded with the silanization reagent are weighed and dispersed in 62.5mL of the mixed solution, and the amide reaction is continuously carried out for 2h at the normal temperature;
(3) After the reaction is finished, sequentially washing the silicon spheres with water and methanol, and carrying out vacuum drying for 10 hours at 50 ℃ to obtain silicon spheres (Sil-GQDs) bonded with the graphene quantum dots for later use;
3. preparing silicon spheres for bonding the graphene quantum dots and the RAFT transfer reagent:
(1) 1.7g of dodecyl trithiocarbonate and 10mg of 4-Dimethylaminopyridine (DMAP) are weighed and dispersed in 100mL of THF, and stirred for 10min to obtain a solution containing a chain transfer agent;
(2) Adding 2.5g of prepared silicon spheres (Sil-GQDs) bonded with graphene quantum dots into 62.5mL of the solution containing the chain transfer agent, stirring for 5min at 35 ℃, then slowly adding 100mg of Dicyclohexylcarbodiimide (DCC), and continuously reacting for 24h at normal temperature (25 ℃);
(3) And after the reaction is finished, filtering, washing the product by using dichloromethane, pure water and methanol in sequence, and drying at 50 ℃ for 10 hours to obtain silica spheres (Sil-GQDs-DMP) bonded with the graphene quantum dots and the RAFT transfer reagent for later use.
4. Preparing a chromatographic packing of the poly (N-isopropylacrylamide) -modified graphene quantum dots:
(1) 150mL of 1, 4-dioxane was used as a solvent, 9g of N-isopropylacrylamide (NIPAM) and 30mg of Azobisisobutyronitrile (AIBN) were added, and mixed uniformly to obtain a mixed solution;
(2) Adding 2.5g of silicon spheres (Sil-GQDs-DMP) bonded with graphene quantum dots and RAFT transfer reagents into 62.5mL of mixed solution, continuously vacuumizing and introducing nitrogen for repeated circulation for 4 times (60 min), and reacting for 2h at 85 ℃;
(3) And after the reaction is finished, filtering, washing the product with tetrahydrofuran, pure water and methanol in sequence, and drying in vacuum at 50 ℃ for 10 hours to obtain the chromatographic packing (Sil-GQDs-PNIPAAm) of the poly (N-isopropylacrylamide) -modified graphene quantum dots.
Elemental analysis is carried out on the activated Silica spheres (Silica) obtained in the preparation process and the chromatographic filler (Sil-GQDs-PNIPAAm) of the final product poly (N-isopropylacrylamide) modified graphene quantum dots, the result is shown in Table 1, and the differences of the content of each element of C, N, H and S between the chromatographic filler (Sil-GQDs-PNIPAAm) and the activated Silica spheres (Silica) in the Table 1 prove that the preparation method successfully bonds functional groups containing C, S and N on the activated Silica spheres.
TABLE 1 elemental analysis results for Silica and Sil-GQDs-PNIPAAm
Respectively carrying out infrared spectrum scanning on intermediate products prepared in the preparation process of chromatographic packing (Sil-GQDs-PNIPAAm) of the poly (N-isopropylacrylamide) modified graphene quantum dots to obtain an infrared spectrogram shown in figure 1, wherein a is activated silicon spheres (Silica); b is silicon spheres bonded with a silanization reagent (Sil-APTES); c is silicon spheres (Sil-GQDs) bonded with the graphene quantum dots; d isSilicon spheres (Sil-GQDs-DMP) bonded with the graphene quantum dots and the RAFT transfer reagent; e is chromatographic packing (Sil-GQDs-PNIPAAm) of the poly (N-isopropylacrylamide) modified graphene quantum dots. The infrared spectrum of the product is 3500cm on the Sil-GQDs-PNIPAAm infrared spectrum in figure 1 -1 、2927cm -1 、2858cm -1 、1548cm -1 、1467cm -1 、1433cm -1 、1338cm -1 And 962cm -1 The characteristic peaks show that the preparation method of the invention can really bond the functional groups of GQDs and PNIPAAm on the porous silicon spheres to obtain the chromatographic packing of the poly (N-isopropylacrylamide) -modified graphene quantum dots.
Thermogravimetric analysis is further carried out on all substances in the preparation process of the chromatographic packing of the poly (N-isopropylacrylamide) modified graphene quantum dot, and the obtained spectrogram is shown in figure 2, wherein a is an activated silicon sphere (Silica); b is silicon spheres (Sil-GQDs) bonded with the graphene quantum dots; c is silicon spheres (Sil-APTES) bonded with a silanization reagent; d is a silicon ball (Sil-GQDs-DMP) bonded with the graphene quantum dot and the RAFT transfer reagent; e is chromatographic packing (Sil-GQDs-PNIPAAm) of the poly (N-isopropylacrylamide) modified graphene quantum dots. Therefore, the preparation method can be further proved to be capable of successfully bonding GQDs and PNIPAAm functional groups on the surface of the porous silicon ball to obtain the chromatographic packing of the poly (N-isopropylacrylamide) -modified graphene quantum dot.
Example 2
The preparation method of the chromatographic packing of the poly (N-isopropylacrylamide) -modified graphene quantum dots comprises the following steps:
1. preparation of silica spheres bound with silylation agent:
(1) Weighing the particles with the particle diameter of 2-10 mu m and the pore diameter of
Performing ultrasonic reaction on 5g of the porous silicon spheres by using 0.1mol/L HCl at 50 ℃ for 24 hours to uniformly disperse the porous silicon spheres, filtering the mixture, washing the mixture to be neutral by using purified water, and drying the mixture at 150 ℃ for 24 hours to obtain activated silicon spheres;
(2) Weighing 2.5g of activated silicon spheres, using dry toluene as a solvent, adding 2mL of 3-Aminopropyltriethoxysilane (APTES), uniformly dispersing, stirring and refluxing for 24h at 20 ℃ under the protection of nitrogen, sequentially filtering and washing a product after the reaction is finished by toluene, pure water and methanol, and performing vacuum drying for 10h at 50 ℃ to obtain silicon spheres (Sil-APTES) bonded with a silanization reagent for later use.
2. Preparing silicon spheres bonded with the graphene quantum dots:
(1) Adding 0.3g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS) into 150mL of dispersion liquid formed by graphene oxide quantum dots (with the particle size of 1-100 nm) and water, wherein the concentration of the graphene oxide quantum dots is 3mg/mL, and stirring for reacting for 10min to activate carboxyl to obtain mixed liquid;
(2) Then 2.5g of prepared silicon spheres (Sil-APTES) bonded with the silanization reagent are weighed and dispersed in 12.5mL of the mixed solution, and the amide reaction is continuously carried out for 24 hours at normal temperature;
(3) After the reaction is finished, sequentially washing the silicon spheres with water and methanol, and carrying out vacuum drying for 2h at 100 ℃ to obtain silicon spheres (Sil-GQDs) bonded with the graphene quantum dots for later use;
3. preparing silicon spheres for bonding the graphene quantum dots and the RAFT transfer reagent:
(1) 1.7g of dodecyl trithiocarbonate and 0.05mg of 4-Dimethylaminopyridine (DMAP) are weighed and dispersed in 50mL of THF, and stirred for 10min to obtain a solution containing a chain transfer agent;
(2) Adding 2.5g of prepared silicon spheres (Sil-GQDs) bonded with graphene quantum dots into 12.5mL of the solution containing the chain transfer agent, stirring for 20min at 25 ℃, slowly adding 166.7mg of Dicyclohexylcarbodiimide (DCC), and continuously reacting for 2h at 35 ℃;
(3) And after the reaction is finished, filtering, washing the product by using dichloromethane, pure water and methanol in sequence, and drying at 100 ℃ for 2 hours to obtain silicon spheres (Sil-GQDs-DMP) bonded with the graphene quantum dots and the RAFT transfer reagent for later use.
4. Preparing a chromatographic packing of the poly (N-isopropylacrylamide) -modified graphene quantum dots:
(1) 150mL of 1, 4-dioxane was used as a solvent, and 30g of N-isopropylacrylamide (NIPAM) and 75mg of Azobisisobutyronitrile (AIBN) were added and mixed uniformly to obtain a mixed solution;
(2) Adding 2.5g of silicon spheres (Sil-GQDs-DMP) bonded with graphene quantum dots and RAFT transfer reagents into 12.5mL of mixed solution, continuously vacuumizing, introducing nitrogen, repeatedly circulating for 4 times (60 min), and reacting for 24h at 25 ℃;
(3) And after the reaction is finished, filtering, washing the product with tetrahydrofuran, pure water and methanol in sequence, and drying in vacuum at 100 ℃ for 24 hours to obtain the chromatographic packing (Sil-GQDs-PNIPAAm) of the poly (N-isopropylacrylamide) -modified graphene quantum dots.
Similarly, the results of elemental analysis, infrared spectrum scanning and thermogravimetric analysis show that the preparation method in example 2 still achieves the purpose of bonding the functional groups of GQDs and PNIPAAm on the surface of the porous silicon sphere to obtain the chromatographic packing of the poly (N-isopropylacrylamide) -modified graphene quantum dot.
Example 3
Research on the application of the prepared chromatographic packing (Sil-GQDs-PNIPAAm) of the poly (N-isopropylacrylamide) modified graphene quantum dots in a high performance liquid chromatography column:
a high performance liquid chromatography column (the specification of the chromatography column is 4.6mm in inner diameter and 150mm in column length) is prepared by using the chromatographic packing (Sil-GQDs-PNIPAAm) of the poly (N-isopropylacrylamide) modified graphene quantum dots synthesized in the example 1 as a stationary phase and using a high pressure homogenization method.
1. Investigating the retention mechanism of alkylbenzene substances on a stationary phase:
selecting methanol/water (45/55, v/v) as a mobile phase, the flow rate is 0.8mL/min, the detection wavelength is 214nm, the column temperature is 35 ℃, and the obtained chromatogram is shown in figure 3 (wherein 1 is toluene, 2 is ethylbenzene, 3 is N-propylbenzene, 4 is butylbenzene, and 5 is N-pentylbenzene), and the difference of delay time of different alkylbenzene compounds proves that the chromatographic filler (Sil-GQDs-PNIPAAm) of the poly (N-isopropylacrylamide) modified graphene quantum dots can detect and separate different alkylbenzene compounds when being used as a fixed phase in a high performance liquid chromatography column.
2. The retention mechanism of polycyclic aromatic hydrocarbon substances on a stationary phase is investigated:
selecting methanol/water (62/38, v/v) as a mobile phase, the flow rate is 0.8mL/min, the detection wavelength is 254nm, the column temperature is 35 ℃, and the obtained chromatogram is shown in figure 4 (wherein 1 is naphthalene, 2 is acenaphthene, 3 is phenanthrene, 4 is pyrene, and 5 is chrysene), and the difference of delay time of different polycyclic aromatic hydrocarbon compounds proves that the chromatographic filler (Sil-GQDs-PNIPAAm) of the poly (N-isopropylacrylamide) modified graphene quantum dot can detect and separate different polycyclic aromatic hydrocarbon compounds when the chromatographic filler is used as a stationary phase in a high performance liquid chromatography column.
3. The retention mechanism of nucleoside and nucleoside base substances on a stationary phase is investigated:
selecting acetonitrile/water (87/13, v/v) as a mobile phase, wherein the flow rate is 0.8mL/min; the detection wavelength is 254nm; the column temperature is 35 ℃, the chromatogram for separating nucleoside and nucleoside base substances is shown in figure 5 (wherein 1 is thiourea, 2 is thymidine, 3 is deoxyadenosine, 4 is adenosine, 5 is uridine, 6 is cytidine, and 7 is cytosine), and the difference of delay times of different nucleoside and nucleoside base substances proves that the chromatographic packing (Sil-GQDs-PNIPAAm) of the poly (N-isopropylacrylamide) modified graphene quantum dot can detect and separate different nucleoside and nucleoside base substances when the chromatographic packing is used as a stationary phase in a high performance liquid chromatography column.
4. The retention mechanism of the phenols on the stationary phase is investigated:
selecting methanol/water (35/65, v/v) as a mobile phase, wherein the flow rate is 0.8mL/min; the detection wavelength is 254nm; the chromatographic chart of separating phenols is shown in fig. 6 (wherein 1 is hydroquinone, 2 is o-nitrophenol, and 3 is p-nitrophenol) at the column temperature of 35 ℃, and the difference of delay times of different phenols proves that the chromatographic packing (Sil-GQDs-PNIPAAm) of the poly (N-isopropylacrylamide) -modified graphene quantum dots can detect and separate different phenols when used as a fixed phase in a high performance liquid chromatography column.
5. Investigating the retention mechanism of aniline substances on a stationary phase:
selecting methanol/water (40/60, v/v) as a mobile phase; the flow rate is 0.8mL/min; the detection wavelength is 254nm; the column temperature is 35 ℃, the chromatogram of the separated aniline substances is shown in fig. 7 (wherein 1 is p-phenylenediamine, 2 is o-phenylenediamine, 3 is biphenyldiamine, 4 is 1-naphthylamine, 5 is 2, 4-dinitroaniline, and 6 is diphenylamine), and the chromatographic filler (Sil-GQDs-PNIPAAm) of the poly (N-isopropylacrylamide) modified graphene quantum dots can detect and separate different aniline compounds when the chromatographic filler is used as a stationary phase in a high performance liquid chromatography column according to the difference of delay times of the different aniline compounds.
6. The chromatographic packing (Sil-GQDs-PNIPAAm) of the poly (N-isopropylacrylamide) modified graphene quantum dots is used as a stationary phase in a high performance liquid chromatography column for separating hydrophilic substances in isatis root particles:
selecting acetonitrile/water (92/8, v/v) as a mobile phase, wherein the flow rate is 0.8mL/min; the UV detection wavelength is 254nm; the column temperature is 35 ℃; detecting hydrophilic substances such as nucleosides in isatis root particles, successfully eluting and separating the nucleosides and syringin in the isatis root particles, and proving that the isatis root particles at least contain four hydrophilic substances including uridine, syringin, adenosine and adenine as shown in figure 8 (wherein 1 is uridine, 2 is syringin, 3 is adenosine, and 4 is adenine), a is the retention time of standard uridine, syringin, adenosine and adenine, and b is the retention time of uridine, syringin, adenosine and adenine separated from traditional Chinese medicine isatis root particles, which shows that chromatographic packing (Sil-GQDs-PNIPAAm) of poly (N-isopropylacrylamide) modified graphene quantum dots can detect and separate the hydrophilic substances such as nucleosides in the isatis root particles when the chromatographic packing is used as a fixed phase in a high performance liquid chromatography column.
In conclusion, the preparation method provided by the invention can bond GQDs and PNIPAAm functional groups on the surface of the porous silicon sphere to obtain the chromatographic packing of the poly (N-isopropylacrylamide) -modified graphene quantum dot. The prepared chromatographic packing is bonded with graphene oxide quantum dots and poly (N-isopropylacrylamide) on the surface of a silicon sphere to form a poly (N-isopropylacrylamide) -modified graphene quantum dot high-performance liquid chromatographic packing, belongs to a mixed-mode high-performance liquid chromatographic packing, has excellent physical structures such as high mechanical strength, good physical and chemical properties and the like of the silica gel packing, has the advantages of high separation speed, high separation selectivity and the like, can make up the defects of a single-mode chromatogram in complex sample analysis, improves the separation efficiency, can be applied to reversed-phase or hydrophilic chromatographic separation, can respectively play a role in reversed-phase/hydrophilic action when being used as a fixed phase of the high-performance liquid chromatographic separation, plays a good role in separating corresponding substances, and can realize the rapid and effective separation of hydrophilic substances such as nucleosides in an actual system.
Finally, the above embodiments are only intended to illustrate the technical solutions of the present invention and not to limit the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all of them should be covered by the claims of the present invention.
Claims (10)
1. A chromatographic filler of poly (N-isopropylacrylamide) -modified graphene quantum dots, wherein the chromatographic filler comprises silicon spheres and graphene quantum dots and poly (N-isopropylacrylamide) bonded on the surfaces of the silicon spheres;
the chromatographic packing is prepared according to the following steps:
(1) Bonding graphene quantum dots on the surface of the silicon spheres: carrying out amidation reaction on the graphene oxide quantum dots on the surfaces of the silicon spheres bonded with the silanization reagent to generate an amide bonding material, namely the silicon spheres bonded with the graphene quantum dots;
(2) Continuously bonding a RAFT transfer reagent on the surface of the silicon ball bonded with the graphene quantum dot: carrying out esterification reaction on the surface of the silicon ball bonded with the graphene quantum dot in the step (1) by using an RAFT (reversible addition-fragmentation chain transfer) reagent to obtain the silicon ball bonded with the graphene quantum dot and the RAFT reagent;
(3) Bonding poly (N-isopropylacrylamide) on the silicon spheres of the bonded graphene quantum dots and RAFT transfer reagent: and (3) carrying out reversible addition-fragmentation chain transfer polymerization reaction on the surface of the silicon ball bonded with the graphene quantum dot and the RAFT transfer reagent in the step (2) by using N-isopropylacrylamide, so as to obtain the chromatographic packing of the poly (N-isopropylacrylamide) -modified graphene quantum dot.
2. A method of preparing a chromatography packing material as claimed in claim 1, characterized in that the method comprises the steps of:
(1) Bonding graphene quantum dots on the surface of the silicon sphere: carrying out amidation reaction on the graphene oxide quantum dots on the surfaces of the silicon spheres bonded with the silanization reagent to generate an amide bonding material, namely the silicon spheres bonded with the graphene quantum dots;
(2) Continuously bonding a RAFT transfer reagent on the surface of the silicon ball bonded with the graphene quantum dot: carrying out esterification reaction on the RAFT transfer reagent on the surface of the silicon ball bonded with the graphene quantum dot in the step (1) to obtain the silicon ball bonded with the graphene quantum dot and the RAFT transfer reagent;
(3) Bonding poly (N-isopropylacrylamide) on the silicon spheres of the bonded graphene quantum dots and RAFT transfer reagent: and (4) carrying out reversible addition-fragmentation chain transfer polymerization reaction on the surface of the silicon ball bonded with the graphene quantum dot and the RAFT transfer reagent in the step (3) by using N-isopropylacrylamide to obtain the chromatographic packing of the poly (N-isopropylacrylamide) modified graphene quantum dot.
3. The production method according to claim 2, wherein the silica spheres bonded with the silylation agent in the step (1) are produced as follows:
a. activating the porous silicon spheres by acid to obtain activated silicon spheres;
b. and (3) carrying out amination treatment on the surface of the activated silicon sphere by using a silylation reagent to obtain the silicon sphere bonded with the silylation reagent.
4. The method according to claim 3, wherein the porous silica spheres have a particle diameter of 2 to 10 μm and a pore diameter of
The silanization reagent is 3-aminopropyl triethoxysilane.
5. The preparation method according to claim 2, wherein the step (1) of bonding the graphene quantum dots on the surface of the silicon sphere comprises the following specific steps:
a. preparing a dispersion solution from graphene oxide quantum dots with the particle size of 1-100 nm and water according to the mass-volume ratio of 1-3;
b. adding the silicon spheres bonded with the silanization reagent into the mixed solution according to the volume mass ratio of 5-25;
c. and after the reaction is finished, filtering, washing with water and methanol in sequence, and drying in vacuum for 5-24 h at normal temperature or 2-10 h at 50-100 ℃ to obtain the silicon spheres bonded with the graphene quantum dots.
6. The preparation method according to claim 2, wherein the step (2) of continuously bonding a RAFT transfer reagent on the surface of the silicon spheres bonded with the graphene quantum dots comprises the specific steps of:
a. adding dodecyl trithiocarbonate and 4-dimethylamino pyridine into a tetrahydrofuran solvent to form a solution containing a chain transfer agent, wherein the volume mass ratio of the tetrahydrofuran solvent to the dodecyl trithiocarbonate to the 4-dimethylamino pyridine is 500-1000;
b. adding the silicon spheres bonded with the graphene quantum dots into the solution containing the chain transfer agent according to the volume-mass ratio of 5-25, 1,mL;
c. and filtering after the reaction is finished, washing with dichloromethane, pure water and methanol in sequence, and drying in vacuum for 5-24 h at normal temperature or 2-10 h at 50-100 ℃ to obtain the silicon spheres bonded with the graphene quantum dots and the RAFT transfer reagent.
7. The preparation method according to claim 2, wherein the step (3) of bonding the poly (N-isopropylacrylamide) on the silicon spheres bonded with the graphene quantum dots and the RAFT transfer reagent comprises the following specific steps:
a. adding azobisisobutyronitrile and N-isopropyl acrylamide into a 1, 4-dioxane solvent according to the volume mass ratio of 10-50;
b. adding the silicon spheres bonded with the graphene quantum dots and the RAFT transfer reagent into the mixed solution according to the volume-mass ratio of 5-25 g to 1,mL, vacuumizing, introducing nitrogen for 30-60min, and reacting for 2-24 h at 25-85 ℃;
c. and after the reaction is finished, filtering, washing with tetrahydrofuran, pure water and methanol in sequence, and performing vacuum drying at normal temperature for 5-24 hours or at 50-100 ℃ for 2-10 hours to obtain the chromatographic packing of the poly (N-isopropylacrylamide) -modified graphene quantum dots, wherein poly (N-isopropylacrylamide) is bonded on silicon spheres bonded with the graphene quantum dots and the RAFT transfer reagent.
8. The application of the chromatographic packing of the poly (N-isopropylacrylamide) -modified graphene quantum dots in the high performance liquid chromatography column in claim 1.
9. Use according to claim 8, wherein the use is a hydrophilic chromatography separation or a reverse phase chromatography separation.
10. Use according to claim 9, wherein the hydrophilic chromatographic separation is in particular: the chromatographic packing of the poly (N-isopropylacrylamide) -modified graphene quantum dots is used as a stationary phase of a high performance liquid chromatography column for rapidly detecting or separating hydrophilic substances, wherein the hydrophilic substances are nucleosides, nucleoside bases, water-soluble vitamins or amino acid substances;
the reversed phase chromatographic separation specifically comprises the following steps: the chromatographic packing of the poly (N-isopropylacrylamide) modified graphene quantum dots is used as a stationary phase of a high performance liquid chromatography column for rapidly detecting or separating benzene, biphenyl, polycyclic aromatic hydrocarbon, aniline or phenol substances containing different numbers of carbon atom alkyl chain substitutions.
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