Silica microspheres containing a mercapto shell, their preparation and use in chromatographic stationary phases
By constructing a thiol shell on the surface of non-porous silica microspheres to form core-shell C30 hybrid microspheres, the problem of limited separation effect of existing C18 chromatographic stationary phases for strongly hydrophobic compounds is solved, and efficient separation of weakly polar and hydrophobic compounds is achieved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- NORTHWEST UNIV
- Filing Date
- 2024-11-27
- Publication Date
- 2026-05-29
AI Technical Summary
Existing core-shell C18 chromatographic stationary phases have limited separation performance against strongly hydrophobic compounds and are difficult to effectively separate weakly polar and hydrophobic compounds.
A thiol shell was constructed on the surface of non-porous silica microspheres using a sol-gel reaction to form core-shell C30 hybrid microspheres. Thiol functional groups were then used to modify the core-shell C30 chromatographic stationary phase, which enhanced hydrophobicity and molecular recognition ability.
It improves chromatographic separation efficiency, effectively separates weakly polar and hydrophobic compounds, reduces longitudinal molecular diffusion, enhances hydrophobicity and molecular shape recognition capabilities, and achieves good peak shape and separation effect.
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Figure CN122102140A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to silica microspheres containing a thiol shell, their preparation, and their application in chromatographic stationary phases. Specifically, using non-porous silica microspheres as a matrix and (3-mercaptopropyl)triethoxysilane and tetraethyl silicate as functional monomers, a radioactive thiol shell is constructed on the surface of the non-porous silica microspheres via a sol-gel reaction, thus preparing core-shell hybrid silica microspheres. The numerous thiol functional groups in the shell can be directly modified with 1-triaconene to form core-shell C30 hybrid microspheres. These microspheres can be used as chromatographic stationary phases for the separation of weakly polar and hydrophobic compounds. Background Technology
[0002] Chromatographic packing materials have continuously evolved to the most widely used core-shell type, which is an important advancement in chromatographic packing materials and has significant application value in many scientific and technological fields, thus attracting widespread attention from researchers. The development of silicon-based materials has progressed from amorphous silica gel to non-porous spherical silica gel, fully porous spherical silica gel, and further to core-shell silica gel. Compared with other packing materials, core-shell packing materials are composed entirely of an ultrapure solid silica gel core and a radial pore structure with a certain shell thickness. The presence of solid spheres reduces the pore volume of the packing material and reduces the longitudinal diffusion of molecules; in addition, the substances to be separated only undergo solid-liquid partitioning on the shell, which also shortens the path of solute diffusion. Therefore, the special shell structure of core-shell chromatographic packing materials determines its high chromatographic performance (Reference 1. Zhao Xingyun, "Preparation of core-shell silicon-carbon composite microsphere stationary phase and its application in carbohydrate separation", Chromatography, 2020, 38(12):1357-1362).
[0003] In recent years, the demand for stationary phases with excellent chromatographic performance has been increasing. Compared with fully porous silica gel columns, core-shell chromatographic columns have shorter analysis time, increased resolution, and significantly improved separation ability. Currently, the core-shell C18 chromatographic stationary phase is widely used in the market. However, for strongly hydrophobic substances such as lutein and carotene, the separation effect of C18 chromatographic stationary phase is limited. Compared with C18, C30 chromatographic stationary phase has a longer hydrophobic alkyl chain, which is more hydrophobic. It can form a dense multilayer C30 alkyl chain on the silica gel surface, which can more effectively mask the silanol groups on the silica gel surface. At the same time, it has a stronger solute retention capacity and less non-specific adsorption for strongly polar substances. Therefore, it has a higher retention capacity and resolution for non-polar solutes and has a very good separation ability (Reference 2. Lin Yang, “Analysis and determination of abamectin residue in vegetables by HPLC method of C30 chromatographic column” Food Industry, 2022, 43(11):110136). Summary of the Invention
[0004] The purpose of this invention is to provide a silica microsphere containing a thiol shell, its preparation, and its application in chromatographic stationary phases.
[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows:
[0006] (1) Preparation of monodisperse hybrid silica microspheres containing thiol shells
[0007] First, weigh 2.0–4.0 g of non-porous silica microspheres, 2.0–4.0 g of N,N-diethanoldodecylamide and 0.2–0.4 g of N-(2,3-dioleoyloxy)propyl-N,N,N-trimethylamine (chloride) into container A, disperse them in 70–150 mL of deionized water, and ultrasonically disperse and mix them. Then, 2.0–4.0 g of urea was added to container A and stirred at 200–500 rpm for 10–30 min at room temperature. Next, 70–150 mL of toluene, 1.5–3.0 mL of isopropanol, 2.0–4.0 mL of tetraethyl silicate, and 2.0–4.0 mL of (3-mercaptopropyl)triethoxysilane were measured and added to container B. The stirring speed was then adjusted to 100–300 rpm, and the solution in container B was poured into container A. The temperature was raised to 50–120 °C, and the reaction was carried out for 10–24 h. Finally, the mixture was dried in a vacuum drying oven at 50–80 °C for 12–24 h to obtain monodisperse hybrid silica microspheres containing a thiol shell.
[0008] (2) Preparation of monodisperse core-shell type C30 stationary phase
[0009] Take 1.0–2.0 g of dried thiol-shell core-shell microspheres in a single-necked flask, weigh 1.0–2.0 g of 1-triaconene, add 50–100 mL of toluene, sonicate for 3–5 min, heat under reflux at 100–130 °C for 12–24 h, wash, and dry in a vacuum drying oven at 60 °C for 12–24 h to obtain a thiol-functionalized core-shell C30 chromatographic stationary phase.
[0010] The preparation method used in this invention is low-cost, involves few steps, and has mild reaction conditions, making it suitable for large-scale preparation. The resulting hybrid microspheres have a large number of thiol functional groups in their shells, which facilitates subsequent functionalization modifications. The good monodispersity and unique core-shell structure of the microspheres make them very suitable as stationary phases for liquid chromatography.
[0011] The present invention has the following advantages:
[0012] 1. The preparation process of this material is simple, the raw materials are readily available, and the cost is low.
[0013] 2. The material has a core-shell structure. Due to the presence of a solid core, the pore volume of the packing material is reduced, which can reduce the longitudinal diffusion of molecules; the diffusion distance of the solute is reduced, which can effectively reduce the mass transfer resistance and thus improve the chromatographic separation efficiency.
[0014] 3. Core-shell C30 chromatographic stationary phases have strong hydrophobicity and a high molecular shape tolerance.
[0015] It has good recognition ability and peak shape, and can effectively separate weakly polar compounds and hydrophobic compounds. Attached Figure Description
[0016] Figure 1 This is a schematic diagram illustrating the preparation of monodisperse hybrid silica microspheres containing a thiol shell and a C30 chromatographic stationary phase.
[0017] Figure 2 The images show (a) scanning electron microscope (SEM) and (b) transmission electron microscope (TEM) images of the non-porous silica microspheres in Example 1, and (c, d) SEM and (e, f) TEM images of SiO2@SiO2-thiol-1.
[0018] Figure 3 The figures show (a) N2 adsorption / desorption curves and (b) pore size distribution of SiO2@SiO2-thiol-1 in Example 1.
[0019] Figure 4 The image shows the infrared spectrum of SiO2@SiO2-thiol-1 in Example 1.
[0020] Figure 5 The chromatogram of C30-1 separating benzene compounds in Example 1 is as follows: the elution order is (1) thiourea, (2) benzene, (3) toluene, (4) ethylbenzene, (5) propylbenzene, and (6) butylbenzene.
[0021] Figure 6 The images show (a, b) scanning electron microscope (SEM) and (c, d) transmission electron microscope (TEM) images of SiO2@SiO2-thiol-2 in Example 2.
[0022] Figure 7 The figures show (a) N2 adsorption / desorption curves and (b) pore size distribution of SiO2@SiO2-thiol-2 in Example 2.
[0023] Figure 8 The chromatogram of C30-2 separating benzene compounds in Example 2 is as follows: the elution order is (1) thiourea, (2) benzene, (3) toluene, (4) ethylbenzene, (5) propylbenzene, and (6) butylbenzene.
[0024] Figure 9 The images show (a, b) scanning electron microscope (SEM) and (c, d) transmission electron microscope (TEM) images of SiO2@SiO2-thiol-3 in Example 3.
[0025] Figure 10The figures show (a) N2 adsorption / desorption curves and (b) pore size distribution of SiO2@SiO2-thiol-3 in Example 3.
[0026] Figure 11 The chromatogram of C30-3 separating benzene compounds in Example 3 is as follows: the elution order is (1) thiourea, (2) benzene, (3) toluene, (4) ethylbenzene, (5) propylbenzene, and (6) butylbenzene.
[0027] Figure 12 The images show (a, b) scanning electron microscope (SEM) and (c, d) transmission electron microscope (TEM) images of SiO2@SiO2-thiol-4 in Example 4.
[0028] Figure 13 The figures show (a) N2 adsorption / desorption curves and (b) pore size distribution of SiO2@SiO2-thiol-4 in Example 4.
[0029] Figure 14 The chromatogram of C30-4 separating benzene compounds in Example 4 is as follows: the elution order is (1) thiourea, (2) benzene, (3) toluene, (4) ethylbenzene, and (5) propylbenzene.
[0030] Figure 15 The chromatogram for the separation of benzene series compounds by C18-1 in Comparative Example 1 is as follows: the peak order is (1) thiourea, (2) benzene, (3) toluene, (4) ethylbenzene, and (5) propylbenzene. Detailed Implementation
[0031] Example 1: Monodisperse hybrid silica microspheres containing thiol shells and their application in C30 chromatographic stationary phase.
[0032] (1) Preparation of monodisperse hybrid silica microspheres containing thiol shells:
[0033] Preparation of self-made non-porous silica microspheres (particle size range 2.3–2.5 μm): First, weigh 0.3 g of potassium chloride and add it to a three-necked flask; then measure 152 mL of ammonia water with a mass concentration of 25–28% and 1072 mL of anhydrous ethanol, and sonicate to mix them evenly; then measure 200 mL of tetraethyl silicate and 500 mL of anhydrous ethanol into a beaker, sonicate for 15 min, and then slowly add them dropwise to the flask using a peristaltic pump; set the temperature to 50 °C and the mechanical stirring speed to 200 rpm; after the addition is complete, continue the reaction for 3 h, then centrifuge and wash. After washing, place them in a vacuum drying oven at 80 °C and dry for 8 h to obtain solid silica microspheres with smooth and non-porous surfaces (particle size range 2.3–2.5 μm);
[0034] Preparation of monodisperse hybrid silica microspheres containing a thiol shell: First, weigh 2.0 g of nonporous silica microspheres, 3.0 g of N,N-diethanoldodecanoic acid and 0.3 g of N-(2,3-dioleoyloxy)propyl-N,N,N-trimethylamine (chloride salt) into a three-necked flask, disperse in 100 mL of deionized water, and ultrasonically disperse and mix. Then, add 2.0 g of urea to the flask sequentially, and stir at 300 rpm for 20 min at room temperature. Measure 100 mL of toluene, 2.0 mL of isopropanol, and...
[0035] 2.0 mL of tetraethyl silicate and 4.0 mL of (3-mercaptopropyl)triethoxysilane were added to a small beaker. The stirring speed in the flask was then adjusted to 100 rpm, and the solution in the beaker was poured into the flask. The temperature was raised to 70 °C, and the reaction was carried out for 24 h. After centrifugation and washing, the solution was placed in a vacuum drying oven at 80 °C and dried for 8 h. The monodisperse hybrid silica microspheres containing a thiol shell were named SiO2@SiO2-thiol-1.
[0036] (2) Preparation of core-shell C30 stationary phase
[0037] Take 2.0 g of dried microspheres SiO2@SiO2-thiol-1 into a two-necked flask, then weigh 2.0 g of 1-triaconene, add 100 mL of toluene, sonicate for 3 min, heat under reflux at 120 °C for 24 h, wash, and dry in a vacuum drying oven at 60 °C for 12 h to obtain the C30-modified core-shell chromatographic stationary phase, named C30-1.
[0038] Product characterization
[0039] Scanning electron microscopy results show that, Figure 2 Figures ab show the self-made non-porous silica microspheres, which are monodisperse with a uniform particle size distribution (2.3–2.5 μm) and a smooth surface; Figure 2 As shown in cf, the SiO2@SiO2-thiol-1 microspheres are monodisperse with a uniform particle size distribution in the range of 2.4 to 2.7 μm. The surface of the microspheres is rough and has obvious pore structure. Figure 2 f is a transmission electron microscope (TEM) image of SiO2@SiO2-thiol-1. The image shows that the microspheres possess a complete core-shell structure with a shell thickness of 80–90 nm. The hybrid microspheres exhibit a core-shell structure, with pores on the surface shell radially distributed around a non-porous silica microsphere core, indicating a radially porous surface shell structure. The shell surface is uniformly hybridized with thiol groups.
[0040] Figure 3 The results show the nitrogen adsorption / desorption experiments of SiO2@SiO2-thiol-1. The specific surface area of SiO2@SiO2-thiol-1 is 52.0 m².2 / g, pore size is mainly distributed in
[0041] Figure 4 This is the infrared spectrum of SiO2@SiO2-thiol-1. A value of 1098 cm⁻¹ appears in the spectrum. -1 and 806cm -1 The strong absorption peaks at 3450 cm⁻¹ correspond to the asymmetric and symmetric stretching vibrations of Si-O-Si bonds in the matrix, respectively; -1 The strong characteristic absorption is a characteristic peak of the Si-OH bond; 2925 cm⁻¹ -1 and 2854cm -1 The strong characteristic absorption peak at the point indicates the presence of a methylene group originating from C30.
[0042] Product Application
[0043] C30-1 was used as the stationary phase in liquid chromatography for the separation and analysis of benzene series compounds (including benzene, toluene, ethylbenzene, propylbenzene, and butylbenzene). The instrument used was an APUS-type ultra-high performance liquid chromatograph from Chengdu Kerui Technology Co., Ltd.; column size: 4.6 × 50 mm; mobile phase: acetonitrile / water, 50 / 50 (v / v); flow rate: 1.0 mL / min; column pressure: 10.2 MPa; UV detector wavelength: 254 nm.
[0044] Evaluation results
[0045] Figure 5 The results of liquid chromatography analysis of benzene series compounds on C30-1 are as follows: (1) thiourea (0.18 min), (2) benzene (0.69 min), (3) toluene (1.14 min), (4) ethylbenzene (1.91 min), (5) propylbenzene (3.48 min), and (6) butylbenzene (6.35 min). The five benzene series compounds were analyzed and detected within 7 min, with good separation reaching baseline. The column efficiency for ethylbenzene was 80980 / m; the resolution of ethylbenzene against toluene was 7.99, indicating that C30-1 has good selectivity for methylene groups.
[0046] Example 2: Monodisperse hybrid silica microspheres containing thiol shells and their application in C30 chromatographic stationary phase.
[0047] In the preparation of the hybrid silica microspheres in Example 1, the amounts of tetraethyl silicate and (3-mercaptopropyl)triethoxysilane were adjusted to 3.0 mL each. The remaining preparation steps (process and conditions) were the same as those in Example 1 for the C30-1 modification process. The obtained monodisperse hybrid silica microspheres containing a thiol shell were named SiO2@SiO2-thiol-2, and the core-shell chromatographic stationary phase modified with C30 was named C30-2.
[0048] Product characterization
[0049] Scanning electron microscopy results show that, Figure 6 As shown in ab, the SiO2@SiO2-thiol-2 microspheres are monodisperse with a uniform particle size distribution in the range of 2.7 to 3.0 μm, and the surface of the microspheres has obvious pore structures. Figure 6 cd is a transmission electron microscope (TEM) image of SiO2@SiO2-thiol-2. The image clearly shows that the microspheres have a distinct core-shell structure with a shell thickness of 190–210 nm. Comparing with Example 1, it can be inferred that increasing the amount of tetraethyl silicate and decreasing the amount of (3-mercaptopropyl)triethoxysilane in the raw materials significantly increases the shell thickness of the prepared SiO2@SiO2-thiol-2.
[0050] Figure 7 The results show the nitrogen adsorption / desorption experiments of SiO2@SiO2-thiol-2. The specific surface area of SiO2@SiO2-thiol-2 is 77.0 m². 2 / g, pore size is mainly distributed in Compared with Example 1, due to the increased shell thickness containing the porous structure, the specific surface area of SiO2@SiO2-thiol-2 is significantly improved compared with SiO2@SiO2-thiol-1.
[0051] Product Application
[0052] C30-2 was used as the stationary phase in liquid chromatography for the separation and analysis of benzene series compounds (benzene, toluene, ethylbenzene, propylbenzene, and butylbenzene). The analytical conditions were the same as in Example 1, with a column pressure of 10.9 MPa.
[0053] Evaluation results
[0054] Figure 8 The results of liquid chromatography analysis of benzene series compounds on C30-2 are as follows: (1) thiourea (0.27 min), (2) benzene (1.10 min), (3) toluene (1.81 min), (4) ethylbenzene (3.04 min), (5) propylbenzene (5.67 min), and (6) butylbenzene (10.70 min). The five benzene series compounds were analyzed and detected within 11 min, with good separation reaching baseline. The column efficiency for ethylbenzene was 83,376 / m; the resolution of ethylbenzene against toluene was 8.13. Compared with Example 1, the retention times of benzene series compounds on C30-2 were significantly increased, and the separation column efficiency was also enhanced. This may be attributed to the thicker shell of SiO2@SiO2-thiol-2, which can bind more C30 functional groups, thus making C30-2 more hydrophobic, enhancing the hydrophobic interaction with benzene series compounds, resulting in enhanced retention and selectivity.
[0055] Example 3: Monodisperse hybrid silica microspheres containing thiol shells and their application in C30 chromatographic stationary phase.
[0056] In the preparation of hybrid silica microspheres in Example 1, the amount of silane reagent was adjusted. The amount of tetraethyl silicate was increased to 4.0 mL, and the amount of (3-mercaptopropyl)triethoxysilane was further reduced to 2.0 mL. The remaining steps (process and conditions) were the same as in Example 1 for the C30-1 modification process. The obtained monodisperse hybrid silica microspheres containing a thiol shell were named SiO2@SiO2-thiol-3, and the core-shell chromatographic stationary phase modified by C30 was named C30-3.
[0057] Product characterization
[0058] Scanning electron microscopy results show that, Figure 9 As shown in ab, the SiO2@SiO2-thiol-3 microspheres are monodisperse with a uniform particle size distribution, but a very small number of nanoparticles are present. The particle size distribution is in the range of 2.3 to 2.6 μm. The surface of the microspheres is rough and has a porous structure. Figure 9 cd is a transmission electron microscope (TEM) image of SiO2@SiO2-thiol-3. The image clearly shows that the microspheres have a core-shell structure with a relatively thin shell thickness of 40–45 nm. Figure 10 The results show the nitrogen adsorption / desorption experiments on SiO2@SiO2-thiol-3. The specific surface area of SiO2@SiO2-thiol-3 is 45.0 m². 2 / g, pore size is mainly distributed in
[0059] Comparing Examples 1, 2, and 3, as the amount of tetraethyl silicate in the raw materials increased and the amount of (3-mercaptopropyl)triethoxysilane decreased, the shell thickness of the hybrid microspheres first increased and then decreased, indicating that adjusting the ratio of the two will seriously affect the shell thickness, and thus affect the specific surface area of the hybrid microspheres.
[0060] Product Application
[0061] C30-3 was used as the stationary phase in liquid chromatography for the separation and analysis of benzene series compounds (benzene, toluene, ethylbenzene, propylbenzene, and butylbenzene). The analytical conditions were the same as in Example 1, with a column pressure of 9.8 MPa.
[0062] Evaluation results
[0063] Figure 11The results of liquid chromatography analysis of benzene series compounds on C30-3 are as follows: (1) thiourea (0.16 min), (2) benzene (0.382 min), (3) toluene (0.53 min), (4) ethylbenzene (0.76 min), (5) propylbenzene (1.19 min), and (6) butylbenzene (1.91 min). The five benzene series compounds were analyzed and detected within 2.5 min, showing good separation and achieving baseline separation. The column efficiency for ethylbenzene was 64,658 / m; the resolution of ethylbenzene against toluene was 4.62. Compared with Examples 1, 2, and 3, the retention time of benzene series compounds on C30-3 was shortened due to the reduced shell thickness.
[0064] Example 4: Monodisperse hybrid silica microspheres containing thiol shells and their application in C30 chromatographic stationary phase.
[0065] In the preparation of hybrid silica microspheres in Example 1, the amount of silane reagent was further adjusted. The amount of tetraethyl silicate was 3.0 mL, and the amount of (3-mercaptopropyl)triethoxysilane was increased to 8.0 mL. The remaining steps (process and conditions) were the same as in Example 1 for the C30-1 modification process. The resulting hybrid silica microspheres containing a thiol shell were named SiO2@SiO2-thiol-4, and the core-shell chromatographic stationary phase modified by C30 was named C30-4.
[0066] Product characterization
[0067] Scanning electron microscopy results show that, Figure 12 As shown in ab, the SiO2@SiO2-thiol-4 microspheres have poor monodispersity, containing a large number of nanoparticles with a particle size distribution in the range of 2.3 to 2.5 μm. The surface of the microspheres is smooth, and the pore structure is almost invisible. Figure 12 cd is a transmission electron microscope (TEM) image of SiO2@SiO2-thiol-4. No obvious shell structure is observed in the image. Figure 13 The results show the nitrogen adsorption / desorption curves for SiO2@SiO2-thiol-4. The specific surface area of SiO2@SiO2-thiol-4 is 12.0 m². 2 / g, pore size is mainly distributed in
[0068] Comparing Examples 1, 2, and 3, it can be found that when the amount of (3-mercaptopropyl)triethoxysilane in the raw materials exceeds a certain range, core-shell hybrid silica microspheres cannot be obtained.
[0069] Product Application
[0070] C30-4 was used as the stationary phase in liquid chromatography for the separation and analysis of benzene series compounds (benzene, toluene, ethylbenzene, propylbenzene, and butylbenzene). The analytical conditions were the same as in Example 1, with a column pressure of 12.7 MPa.
[0071] Evaluation results
[0072] Figure 14 The results of liquid chromatography analysis of benzene series compounds on C30-4 are as follows: (1) thiourea (0.47 min), (2) benzene (0.75 min), (3) toluene (0.88 min), (4) ethylbenzene (1.08 min), and (5) propylbenzene (1.40 min). The five benzene series compounds showed weak retention within the column, eluting within 2 min. The separation effect was poor, with significant differences between them, far below baseline separation. The column efficiency of ethylbenzene was only 7,200 / m. This can be attributed, on the one hand, to the thin shell of SiO2@SiO2-thiol-4, which lacks sufficient thiol modification sites for C30 binding, resulting in a low number of C30s in the C30-4 shell, leading to weak hydrophobicity and shortened retention time. On the other hand, the presence of numerous tiny nanoparticles significantly reduced the column efficiency of the stationary phase, resulting in weakened selectivity and separation of benzene series compounds.
[0073] Comparative example: Monodisperse hybrid silica microspheres containing thiol shells and their application in C18 chromatographic stationary phases.
[0074] In Example 2, the modification process was adjusted during the preparation of hybrid silica microspheres by replacing 1-triacontene with 1-octadecene, while the remaining steps (process and conditions) remained the same as in Example 2. The resulting C18-modified core-shell chromatographic stationary phase was named C18-1.
[0075] Product Application
[0076] C18-1 was used as the stationary phase in liquid chromatography for the separation and analysis of benzene series compounds (benzene, toluene, ethylbenzene, propylbenzene, and butylbenzene). The analytical conditions were the same as in Example 1, with a column pressure of 11.6 MPa.
[0077] Evaluation results
[0078] Figure 15 The results of liquid chromatography analysis of benzene series compounds on C18-1 are as follows: (1) thiourea (0.55 min), (2) benzene (0.88 min), (3) toluene (1.02 min), (4) ethylbenzene (1.28 min), and (5) propylbenzene (1.55 min). The five benzene series compounds showed weak retention, eluting from the column within 2 min, indicating poor separation and inability to achieve baseline separation. The ethylbenzene and toluene peaks were only slightly distinguishable, but the column efficiency was difficult to measure.
[0079] In comparison, C30-2 showed a good separation effect on benzene series compounds in Example 2. Figure 8 This indicates that, under the same conditions, C30 modification significantly improves the hydrophobicity of the stationary phase compared to C18 modification, thereby enhancing the selectivity and separation effect for weakly polar substances.
Claims
1. A method for preparing monodisperse hybrid silica microspheres containing a thiol shell, characterized in that: Using non-porous silica microspheres as the matrix, (3-mercaptopropyl)triethoxysilane and tetraethyl silicate as functional monomers, and N,N-diethanoldodecylamide and N-(2,3-dioleoyloxy)propyl-N,N,N-trimethylamine (chloride salt) as dual template pore-forming agents, a sol-gel reaction is carried out under the action of urea catalyst to construct a silica shell layer on the surface of non-porous silica microspheres, forming monodisperse hybrid silica microspheres containing a mercapto shell.
2. The preparation method according to claim 1 or 2, characterized in that: You can follow these steps: First, weigh 0.5–8.0 g (preferably 1.0–5.0 g; more preferably 2.0–4.0 g) of non-porous silica microspheres, 0.5–8.0 g (preferably 1.0–5.0 g; more preferably 2.0–4.0 g) of N,N-diethanoldodecanoic acid and 0.1–0.8 g (preferably 0.1–0.5 g; more preferably 0.2–0.4 g) of N-(2,3-dioleoyloxy)propyl- N,N,N-trimethylamine (chloride) is dispersed in container A in 30–400 mL (preferably 50–200 mL; more preferably 70–150 mL) of deionized water and ultrasonically dispersed and mixed. Then, 0.5–8.0 g (preferably 1.0–5.0 g; more preferably 2.0–4.0 g) of urea is added to container A, and the mixture is stirred at 100–600 rpm for 5–30 min at room temperature. Measure 30–400 mL (preferably 50–200 mL; more preferably 70–150 mL) of toluene, 0.5–6.0 mL (preferably 1.0–5.0 mL; more preferably 1.5–3.0 mL) of isopropanol, 0.5–6.0 mL (preferably 1.0–5.0 mL; more preferably 2.0–4.0 mL) of tetraethyl silicate, and 0.5–6.0 mL (preferably 1.0–5.0 mL; more preferably 2.0–4.0 mL) of (3-mercaptopropyl)triethoxysilane and add them to container B. Then, adjust the stirring speed in container A to 50–300 rpm, pour the solution from container B into container A, raise the temperature to 30–120 °C, and react for 8–24 h. Finally, dry in a vacuum drying oven at 30–80 °C for 8–24 h to obtain monodisperse hybrid silica microspheres containing a thiol shell.
3. The preparation method according to claim 1 or 2, characterized in that: The silica microsphere matrix consists of solid silica microspheres with a particle size ranging from 0.2 μm to 5.0 μm.
4. A monodisperse hybrid silica microsphere containing a thiol shell prepared by the preparation method of claim 2 or 3.
5. The microspheres according to claim 4, characterized in that: The hybrid microspheres have a core-shell structure with a radial porous surface shell, and the shell surface is uniformly hybridized with thiol groups.
6. A core-shell C30 chromatographic stationary phase, obtained by direct click reaction of monodisperse hybrid silica microspheres containing a thiol shell as described in any one of claims 4-5 with 1-triacoene, the specific process being as follows: Weigh 0.5–4.0 g of the monodisperse hybrid silica microspheres containing a thiol shell as described in any one of claims 4–5, add 1.0–2.0 g of 1-triacontene, add 50–100 mL of toluene, sonicate for 3–5 min, heat under reflux at 100–150 °C for 12–24 h, wash, and then dry in a vacuum drying oven for 12–24 h.
7. The application of the monodisperse hybrid silica microspheres containing a thiol shell as described in any one of claims 4 to 5, or the core-shell type C30 chromatographic stationary phase as described in claim 6, as a chromatographic stationary phase packing material.
8. The application according to claim 7, characterized in that: The chromatographic stationary phase described in claim 6 can be used as a chromatographic stationary phase packing material for separating one or more weakly polar substances, such as polycyclic aromatic hydrocarbons, carotenoid isomers, etc.