AU2020101112A4 - Carborane-modified mesoporous silica nanosphere (msn) and preparation method thereof - Google Patents
Carborane-modified mesoporous silica nanosphere (msn) and preparation method thereof Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002077 nanosphere Substances 0.000 title claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 39
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 19
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- -1 monosubstituted trimethoxysilylpropyl Chemical group 0.000 claims description 15
- GLISZRPOUBOZDL-UHFFFAOYSA-N 3-bromopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCBr GLISZRPOUBOZDL-UHFFFAOYSA-N 0.000 claims description 12
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 230000002209 hydrophobic effect Effects 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000010791 quenching Methods 0.000 claims description 5
- 230000000171 quenching effect Effects 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- GJLPUBMCTFOXHD-UPHRSURJSA-N (11z)-1$l^{2},2$l^{2},3$l^{2},4$l^{2},5$l^{2},6$l^{2},7$l^{2},8$l^{2},9$l^{2},10$l^{2}-decaboracyclododec-11-ene Chemical compound [B]1[B][B][B][B][B]\C=C/[B][B][B][B]1 GJLPUBMCTFOXHD-UPHRSURJSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 3
- 239000012452 mother liquor Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- JTWJUVSLJRLZFF-UHFFFAOYSA-N 2$l^{2},3$l^{2},4$l^{2},5$l^{2},6$l^{2},7$l^{2},8$l^{2},9$l^{2},11$l^{2},12$l^{2}-decaborabicyclo[8.1.1]dodecane Chemical compound [B]1C2[B]C1[B][B][B][B][B][B][B][B]2 JTWJUVSLJRLZFF-UHFFFAOYSA-N 0.000 claims description 2
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical group CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 claims description 2
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical group CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 claims description 2
- CFNUZRMHHJZBOM-UHFFFAOYSA-N [B]1C2[B][B]C1[B][B][B][B][B][B][B]2 Chemical compound [B]1C2[B][B]C1[B][B][B][B][B][B][B]2 CFNUZRMHHJZBOM-UHFFFAOYSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052796 boron Inorganic materials 0.000 abstract description 9
- 239000002105 nanoparticle Substances 0.000 abstract description 5
- 238000002560 therapeutic procedure Methods 0.000 abstract description 4
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 206010028980 Neoplasm Diseases 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract description 2
- 238000011068 loading method Methods 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- 231100000331 toxic Toxicity 0.000 abstract 1
- 230000002588 toxic effect Effects 0.000 abstract 1
- 238000012986 modification Methods 0.000 description 10
- 230000004048 modification Effects 0.000 description 10
- 238000002329 infrared spectrum Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 4
- 230000003833 cell viability Effects 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000006285 cell suspension Substances 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000001963 growth medium Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 102100026735 Coagulation factor VIII Human genes 0.000 description 1
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 108010087230 Sincalide Proteins 0.000 description 1
- 239000006117 anti-reflective coating Substances 0.000 description 1
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 1
- 230000017531 blood circulation Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010609 cell counting kit-8 assay Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000003501 co-culture Methods 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 125000002519 galactosyl group Chemical group C1([C@H](O)[C@@H](O)[C@@H](O)[C@H](O1)CO)* 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- IZTQOLKUZKXIRV-YRVFCXMDSA-N sincalide Chemical compound C([C@@H](C(=O)N[C@@H](CCSC)C(=O)NCC(=O)N[C@@H](CC=1C2=CC=CC=C2NC=1)C(=O)N[C@@H](CCSC)C(=O)N[C@@H](CC(O)=O)C(=O)N[C@@H](CC=1C=CC=CC=1)C(N)=O)NC(=O)[C@@H](N)CC(O)=O)C1=CC=C(OS(O)(=O)=O)C=C1 IZTQOLKUZKXIRV-YRVFCXMDSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
- A61K41/009—Neutron capture therapy, e.g. using uranium or non-boron material
- A61K41/0095—Boron neutron capture therapy, i.e. BNCT, e.g. using boronated porphyrins
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/50—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates
- A61K47/51—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the non-active ingredient being a modifying agent
- A61K47/52—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the non-active ingredient being a modifying agent the modifying agent being an inorganic compound, e.g. an inorganic ion that is complexed with the active ingredient
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P35/00—Antineoplastic agents
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- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Veterinary Medicine (AREA)
- Medicinal Chemistry (AREA)
- Public Health (AREA)
- Pharmacology & Pharmacy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Epidemiology (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Medicinal Preparation (AREA)
Abstract
The present invention provides a carborane-modified mesoporous silica nanosphere (MSN) and
a preparation method thereof, and belongs to the technical field of nanomaterial. The present
invention first covalently links carborane to the surface of mesoporous silica, and the preparation
method thereof features easy operation and low equipment requirement. Meanwhile, nanoparticles
prepared thereby feature structural stability, controllable hydrophilicity and hydrophobicity, and high
boron content; the modified material is not toxic to organisms, can be applied to drug loading systems,
and further has a potential for using as a boron-containing reagent in boron neutron capture therapy
of tumors.
3/6
HEt2O ~Li
NVHn-C 4H9Li -- ~
FIG. 3
Description
3/6
HEt 2O ~Li
NVHn-C 4H 9Li -- ~
FIG. 3
CARBORANE-MODIFIED MESOPOROUS SILICA NANOSPHERE (MSN) AND PREPARATION METHOD THEREOF TECHNICAL FIELD The present invention relates to the technical field of nanomaterial, and in particular to a preparation method of a carborane-modified mesoporous silica nanosphere (MSN). BACKGROUND Porous materials, as special members for developing various techniques, are widely used in material science. Mesoporous silica is a nontoxic, odorless, pollution-free, and degradable nonmetallic material and one of the most widely studied nano-materials in the field of nano-biomedicine today. Mesoporous silica nanoparticles were first successfully synthesized and reported by the groups of Cai, Mann, and Ostafin. Because of low density, high specific surface area, good biocompatibility, and easy modification of surface groups, mesoporous silica nanoparticles are widely used in catalysis, energy storage, self-cleaning antireflective coating, ultrasensitive sensors based on surface plasma resonance, C02 capture, and biomedicine. To meet application requirements in such fields as chromatographic separation, drug loading, and medical diagnosis, surface modification of mesoporous silica is essential. With high boron content, carborane is nontoxic after specific modification and is thereby highly favored in research on boron neutron capture therapy. Chian-Hui Lai et al. first fully aminated the surface of the mesoporous silica, then modified the surface thereof with trivalent galactosyl ligand, hydrophobically modified mesoporous thereof with trimethylchlorosilane, and adsorbed carborane in mesoporous, enabling it to be used for boron neutron capture therapy; however, the carborane adsorbed in mesoporous in this way are easy to leak during blood circulation of organisms. Eric et al. first initiated atom transfer radical polymerization of both HEMA and MES on the surface of an initiator-modified silica nanosphere, and then conducted functionalization of carborane on both carboxyl and hydroxyl groups of side chains of polymers thereof; such a strategy of indirectly linking carborane to the surface of silica feature complicated steps and readily-broken polymer chains; moreover, the strategy had a far smaller silica surface area used than a MSN. Therefore, the corresponding surface grafting amount was far lower than that of the mesoporous silica. SUMMARY An objective of the present invention is to provide a preparation method of a carborane-modified MSN. The invention first covalently links carborane to the surface of the MSN. Nanoparticles prepared thereby feature structural stability, controllable hydrophilicity and hydrophobicity, high boron content, and good biocompatibility. To achieve the above purpose, the present invention provides the following technical solutions: A preparation method of a carborane-modified mesoporous silica nanosphere (MSN) is provided, where the material to be prepared is obtained by covalently linking monosubstituted alkoxysilylpropyl carborane to an MSN. Preferably, a preparation method of the monosubstituted alkoxysilylpropyl carborane is as follows: dissolving carborane in absolute ether and adding n-butyllithium, stirring for hours, adding (3-bromopropyl)trimethoxysilane thereto, stirring for 20 to 24 h, quenching with water, separating the solution, extracting a product with ether, and conducting rotary evaporation to obtain monosubstituted trimethoxysilylpropyl carborane. Preferably, the carborane may be o-carborane, m-carborane, or p-carborane, and the (3-bromopropyl)trimethoxysilane may be replaced with (3-chloropropyl)trimethoxysilane or (3-chloropropyl)triethoxysilane. Preferably, the carborane/n-butyllithium/(3-bromopropyl)trimethoxysilane molar ratio is 1:(1-1.5):(0.9-1.8). Preferably, the MSN is synthesized from TEOS, CTAC, cyclohexane, alkali, and water. Preferably, for the MSN, a surfactant template is extracted with acid alcohol solution, and the template-removed MSN is subject to ultrasonic dispersion in an organic solvent and is heated with the monosubstituted trimethoxysilylpropyl carborane, followed by separation to obtain a final product. Preferably, the organic solvent may be toluene, ethanol, or acetone. Preferably, the mesoporous silica/monosubstituted trimethoxysilylpropyl carborane molar ratio is 1:(0.01-1.3), where hydrophilic particles are obtained when the molar ratio is 1:(0.01-0.2), and hydrophobic particles are obtained when the molar ratio is 1:(0.2-1.3). Preferably, the preparation method includes the following steps: (a) under nitrogen, dissolving carborane in absolute ether, and cooling to 0°C; adding n-butyllithium dropwise, stirring for hours at room temperature, and cooling to 0°C again; adding (3-bromopropyl)trimethoxysilane, stirring the mixture for 20 h at room temperature, and then quenching with water; extracting mother liquor with ether and concentrating by rotary evaporation to obtain the monosubstituted trimethoxysilylpropyl carborane; (b) adding a given amount of CTAC solution (25 wt%) and TEA in deionized water, slowly stirring for 1 to 2 h, adding a mixture containing TEOS and cyclohexane dropwise thereto; continuing the reaction and stirring for 8 to 16 h at a constant temperature of 60°C; centrifuging to collect a product and washing with water and ethanol three to four times, respectively; subsequently, dispersing in acid alcohol solution for reflux for 18 h to remove CTAC template; centrifuging the resulting product and washing with ethanol three to four times, followed by vacuum drying at 45°C; and (c) ultrasonically dispersing a given amount of silica nanospheres in toluene, adding monosubstituted trimethoxysilylpropyl carborane, stirring for 12 to 24 h at 90 to 100°C, centrifuging and washing with absolute alcohol three to four times, followed by vacuum drying for 6 h. The present invention further provides a carborane-modified MSN prepared by the above preparation method of a carborane-modified MSN. Compared with the prior art, the present invention has the following advantages: 1) Compared with previous methods for having carborane adsorbed on the surface of the MSN and the silica to graft to a polymer containing carborane on side chains, the present invention first covalently links carborane to the surface of the MSN in a stable manner under more simple and feasible reaction conditions. 2) Nanoparticles prepared thereby feature structural stability, controllable hydrophilicity and hydrophobicity, high boron content, and good biocompatibility. Particularly, hydrophilic particles are obtained when a mesoporous silica/monosubstituted trimethoxysilylpropyl carborane molar ratio of is 1:(0.01-0.2), and hydrophobic particles are obtained when the molar ratio is 1:(0.2-1.3). 3) The material prepared has a potential for using in boron neutron capture therapy of tumors. 4) It is more creative that MSNs with higher specific surface area are covalently linked to carborane directly in a simple and feasible manner. 5) a) Carborane is dissolved in absolute ether, mixed with n-butyllithium, and stirred for hours, followed by adding (3-bromopropyl)trimethoxysilane thereto, stirring for 20 to 24 h, quenching with water, separating the solution, extracting a product with ether, and conducting rotary evaporation to obtain monosubstituted alkoxysilylpropyl carborane; b) the MSN is synthesized from TEOS, CTAC, cyclohexane, alkali, and water, and then a surfactant template is then extracted with acid alcohol solution; and (c) the template-removed MSN is subject to ultrasonic dispersion in toluene and is heated with the monosubstituted alkoxysilylpropyl carborane while stirring, followed by separation to obtain a final product. 6) In contrast with the known method, using a novel synthetic route to prepare the monosubstituted trimethoxysilylpropyl carborane does not need any catalyst, and synthetic procedures are simple. BRIEF DESCRIPTION OF DRAWINGS FIG. 1 shows an NMR spectrum of synthetic substance A in Example 1. FIG. 2 shows an SEM image of MSNs prepared in Example 2. FIG. 3 shows a schematic illustration of how mesoporous silica conducts surface modification on carborane in the present invention. FIG. 4 shows an infrared spectrum of the surface of the mesoporous silica after modification of carborane: (a) an infrared spectrum of silica without extraction of surfactant; (b) an infrared spectrum of silica after extraction of surfactant; and (c) an infrared spectrum after modification of carborane. FIG. 5 illustrates cell viability at 12 h after co-culture of MSNs with surface modification of carborane with PANC-1 cells. FIG. 6 illustrates water dispersion of carborane-modified hydrophilic and hydrophobic MSNs obtained when feed ratios of monosubstituted trimethoxysilylpropyl carborane to mesoporous silica are 0.2 (Example 3) and 1.0 (Example 4), respectively. DETAILED DESCRIPTION The present invention is further described in detail below with reference to examples. However, it should not be construed that the subject of the present invention is limited to the following examples, and technologies implemented based on above and content of the present invention all fall within the scope of the present invention. Example 1 Under nitrogen, 300 mg of carborane was dissolved in 9 ml of absolute ether, and cooled to0°C; after adding 1.6 ml of n-butyllithium dropwise, the resulting mixture was stirred for 3 h at room temperature, and cooled to 0°C again; after adding 370 pl of (3-bromopropyl)trimethoxysilane, the mixture was stirred for 25 h at room temperature, and then quenched with water; mother liquor was extracted with 3x 10 ml of ether and concentrated in vacuo to obtain substance A, monosubstituted alkoxysilylpropyl carborane, with a yield of 81%. FIG. 1 depicts: 1 H NMR (400 MHz, CDCl3) 6: 3.54 (s, O-CH3, 9H), 2.25-2.20 (t, Cc-CH2, J=10 Hz, 2H), 1.62-1.53 (m, CH2-CH2-CH2, 2H), 0.61-0.57 (t, CH2-Si, J=8 Hz, 2H) ppm. Notably, chemical shifts of both O-CH3 (9H) and C-H (lH) of o-carborane are 3.54, where therefore there are 10 hydrogen atoms, as depicted in FIG. 1. Example 2 Twenty milliliters of CTAC solution (25 wt%) and 310 mg of TEA was added in 50 ml of deionized water, and slowly stirred for 1 h at 60°C, followed by adding a mixture containing 6 ml of TEOS and 22 ml of cyclohexane dropwise thereto; the reaction was continued while stirring for 12 h at a constant temperature of 60°C; after centrifugation, a product was collected and washed with water and ethanol four times, respectively; subsequently, the product was dispersed in 60 ml of acid alcohol solution for reflux for 18 h to remove CTAC template; the resulting product was centrifuged and washed with ethanol four times, followed by vacuum drying for 12 h at 45°C to obtain mesoporous silica. FIG. 2 reveals that MSNs obtained are uniform in size, with a diameter of 130 to 150 nm. Example 3 Ultrasonically, 60 mg of silica nanospheres were dispersed in 10 ml of toluene, and mixed with mg of substance A, followed by stirring for 14 h at 100°C; the mixture was centrifuged and washed with absolute alcohol four times, followed by vacuum drying for 6 h to obtain carborane-modified hydrophilic mesoporous silica. Example 4 Ultrasonically, 60 mg of silica nanospheres were dispersed in 20 ml of toluene, and mixed with 300 mg of substance A, followed by stirring for 14 h at 100°C; the mixture was centrifuged and washed with absolute alcohol four times, followed by vacuum drying for 6 h to obtain carborane-modified hydrophobic mesoporous silica. FIG. 3 shows a schematic illustration of how mesoporous silica conducts surface modification on carborane. Carborane is first dehydrogenized with n-butyllithium, followed by salt elimination reaction with (3-bromopropyl)trimethoxysilane to obtain substance A; substance A reacts with hydroxyl groups to covalently link to carborane directly, and carborane-modified mesoporous silica is obtained. Dried samples obtained were subject to infrared detection. Detection results are illustrated in FIG. 4. In the infrared spectrum (FIG. 4a), -CH2- vibration peaks of surfactant CTAC can be observed at both 2850 and 2930 cm-1 . After extracting CTAC with acid alcohol solution, the foregoing peaks disappear significantly in the infrared spectrum (FIG. 4b). In the infrared spectrum after modification of carborane (FIG. 4c), a significant B-H stretching vibration is visible at 2596 cm-1; moreover, due to the introduction of a propyl group of (3-bromopropyl)trimethoxysilane, -CH2- vibration peaks reappear at both 2850 and 2930 cm- 1. Therefore, it can be confirmed that carborane is successfully modified on the surface of mesoporous silica. PANC-1 cell line was activated and subcultured, and a concentration of cell suspension was adjusted to 2 x 105 PANC-1 cells/ml. In a 96-well plate, 100 pl of the cell suspension was added to each well and cultured for 12 h under a 5% C02 and 95% air atmosphere at 37°C. Different concentrations of sample solutions (0, 50, 100, 200, 300, 400, 500, and 600 pg/ml) were set up and co-cultured with cells, and six wells were repeated for each concentration. After 12 h, sample-containing culture medium was discarded, and cells were washed with 200 Pl of PBS; 100 pl of culture medium and 10 pL of CCK-8 solution was added into each well and re-cultured for 2 h. Cell viability was measured by a microplate reader. Results are depicted in FIG. 5. Even if the sample concentration is as high as 600 pg/ml, the cell viability is still more than 80%. Therefore, carborane-modified MSNs prepared by the present invention are nontoxic when in use. As shown in FIG. 6, when a feed ratio of monosubstituted trimethoxysilylpropyl carborane to mesoporous silica is 0.2 (Example 3), carborane-modified MSNs obtained are still hydrophilic and uniformly dispersible in water; when the feed ratio of monosubstituted trimethoxysilylpropyl carborane to mesoporous silica is 1.0 (Example 4), carborane-modified MSNs obtained are hydrophobic and difficult to disperse in water. Therefore, it is visible that white powder thereof is unable to be moistened and keep afloat. It should be noted that the above examples are merely intended to describe the technical solutions of the present invention, rather than to limit the present invention. Although the present invention is described in detail with reference to the above examples, persons of ordinary skill in the art should understand that they may still make modifications to the technical solutions described in the above examples or make equivalent replacements to some or all technical features thereof, without departing from the essence of the technical solutions in the examples of the present invention.
Claims (10)
1. A preparation method of a carborane-modified mesoporous silica nanosphere (MSN), wherein the material to be prepared is obtained by covalently linking monosubstituted alkoxysilylpropyl carborane to an MSN.
2. The preparation method of the carborane-modified MSN according to claim 1, wherein a preparation method of the monosubstituted alkoxysilylpropyl carborane is as follows: dissolving carborane in absolute ether and adding n-butyllithium, stirring for hours, adding (3-bromopropyl)trimethoxysilane thereto, stirring for 20 to 24 h, quenching with water, separating the solution, extracting a product with ether, and conducting rotary evaporation to obtain monosubstituted trimethoxysilylpropyl carborane.
3. The preparation method of the carborane-modified MSN according to claim 2, wherein the carborane may be o-carborane, m-carborane, or p-carborane, and the (3-bromopropyl)trimethoxysilane may be replaced with (3-chloropropyl)trimethoxysilane or (3-chloropropyl)triethoxysilane.
4. The preparation method of the carborane-modified MSN according to claim 2, wherein the carborane/n-butyllithium/(3-bromopropyl)trimethoxysilane molar ratio is 1:(1-1.5):(0.9-1.8).
5. The preparation method of the carborane-modified MSN according to claim 1, wherein the MSN is synthesized from TEOS, CTAC, cyclohexane, alkali, and water.
6. The preparation method of the carborane-modified MSN according to any one of claims 1 to , wherein for the MSN, a surfactant template is extracted with acid alcohol solution, and the template-removed MSN is subject to ultrasonic dispersion in an organic solvent and is heated with the monosubstituted trimethoxysilylpropyl carborane, followed by separation to obtain a final product.
7. The preparation method of the carborane-modified MSN according to claim 6, wherein the organic solvent may be toluene, ethanol, or acetone.
8. The preparation method of the carborane-modified MSN according to claim 1, wherein the mesoporous silica/monosubstituted trimethoxysilylpropyl carborane molar ratio is 1:(0.01-1.3), wherein hydrophilic particles are obtained when the molar ratio is 1:(0.01-0.2), and hydrophobic particles are obtained when the molar ratio is 1:(0.2-1.3).
9. The preparation method of the carborane-modified MSN according to claim 1, comprising the following steps:
(a) under nitrogen, dissolving carborane in absolute ether, and cooling to 0°C; adding n-butyllithium dropwise, stirring for hours at room temperature, and cooling to 0°C again; adding (3-bromopropyl)trimethoxysilane, stirring the mixture for 20 h at room temperature, and then quenching with water; extracting mother liquor with ether and concentrating by rotary evaporation to obtain the monosubstituted trimethoxysilylpropyl carborane;
(b) adding a given amount of CTAC solution (25 wt%) and TEA in deionized water, slowly stirring for 1 to 2 h, adding a mixture containing TEOS and cyclohexane dropwise thereto; continuing the reaction and stirring for 8 to 16 h at a constant temperature of 60°C; centrifuging to collect a product and washing with water and ethanol three to four times, respectively; subsequently, dispersing in acid alcohol solution for reflux for 18 h to remove CTAC template; centrifuging the resulting product and washing with ethanol three to four times, followed by vacuum drying at 45°C; and
(c) ultrasonically dispersing a given amount of silica nanospheres in toluene, adding monosubstituted trimethoxysilylpropyl carborane, stirring for 12 to 24 h at 90 to 100°C, centrifuging and washing with absolute alcohol three to four times, followed by vacuum drying for 6 h.
10. A carborane-modified MSN prepared by the preparation method of a carborane-modified MSN according to any one of claims 1 to 9.
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| US7053158B2 (en) * | 2003-09-22 | 2006-05-30 | Agency For Science, Technology And Research | Carborane trianion based catalyst |
| KR20080015209A (en) * | 2006-08-14 | 2008-02-19 | 한국원자력연구원 | O-carboran-1-yl-1,3,5-triazine derivative, a process for the preparation thereof and a pharmaceutical composition comprising the same |
| JP5159125B2 (en) * | 2007-03-09 | 2013-03-06 | 独立行政法人科学技術振興機構 | β-1,3-glucan / carborane complex |
| CN104402441B (en) * | 2014-10-28 | 2016-05-04 | 东华大学 | A kind of low temperature Fast Sintering is prepared the method for boron carbide ceramics material |
| CN106236734A (en) * | 2016-08-26 | 2016-12-21 | 郑州大学 | The preparation of mesoporous silicon oxide/insulin nanoparticles that phenylboric acid is modified and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113244391A (en) * | 2021-04-27 | 2021-08-13 | 上海工程技术大学 | Multi-metal sulfide doped mesoporous silica nano composite particle and preparation and application thereof |
| CN114704975A (en) * | 2022-04-21 | 2022-07-05 | 武汉理工大学 | Passive radiation cooler and preparation method thereof |
| CN114873644A (en) * | 2022-05-10 | 2022-08-09 | 安徽农业大学 | Preparation method of molecular carrier for molecular detection |
| CN114854120A (en) * | 2022-06-09 | 2022-08-05 | 广东安拓普聚合物科技有限公司 | High-temperature-resistant and wear-resistant optical cable material for base station |
| CN114854120B (en) * | 2022-06-09 | 2022-12-13 | 广东安拓普聚合物科技有限公司 | High-temperature-resistant and wear-resistant optical cable material for base station |
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