PH-stimulation response type intelligent nanometer container and preparation method thereof

Abstract

The invention discloses a pH-stimulation response type intelligent nanometer container and a preparation method thereof. The method comprises the following steps of preparing mesoporous silica microspheres; performing dealcoholization on the dried mesoporous silica microspheres and an alkynyl-containing silane coupling agent in dried methylbenzene; preparing 2-bromo-ethyoxyl-2-azido radical-ethyoxyl propane; after the product obtained through dealcoholization is dried in vacuum, performing click chemical reaction on the product, excessive 2-bromo-ethyoxyl-2-azido radical-ethyoxyl propane and the dried N,N-dimethyl formamide to generate a five-membered ring; after the obtained product is dried in vacuum, dispersing the product in a buffer solution of NaH2PO4/Na2HPO4 which contains absorbed molecules, adding amino-beta-cyclodextrin into the buffer solution, and performing substitution reaction to obtain the final product, i.e. the PH-stimulation response type intelligent nanometer container. The pH-stimulation response type intelligent nanometer container provided by the invention is high in sensitivity to pH and simple and convenient in response operation; automatic opening/closing of a valve can be realized; releasing of molecules absorbed in the nanometer container is promoted; the pH-stimulation response type intelligent nanometer container has a good application prospect.

Description

technical field

[0001] The invention belongs to the technical field of material science, in particular to a PH-stimulus responsive intelligent nano container and a preparation method thereof. Background technique

[0002] In the field of cell activity detection, because the pH value in the cell is not uniformly distributed, the pH value of the cytoplasm is about 7.2, and some organelles, such as lysosomes and endoplasmic reticulum, have an internal pH value of about 4.0 to 6.0 , showing weak acidity. Lysosomes contain more than 50 kinds of enzymes, which can be activated in the acidic environment of lysosomes to promote the degradation of proteins in cell metabolism. Once the pH gradient in the lysosome disappears, it is likely that the cell has a functional disorder. Therefore, detecting the change of pH in living cells is very meaningful for the study of cell function and its physiological and pathological processes. Although there have been many reports for monitoring a...

Examples

Embodiment 1

[0040] The preparation method of the PH-stimulus-responsive intelligent nano container of the present invention, the steps are as follows:

[0041] Step 1, preparing mesoporous silica microspheres MCM-41, and vacuum-drying the obtained mesoporous silica microspheres; the preparation process of mesoporous silica microspheres MCM-41 is as follows:

[0042] Dissolve 1.0g of acryloyloxyethyltrimethylammonium chloride (AETAC) in 390ml of deionized water, add 40g of styrene, stir mechanically at room temperature for 30min, then raise the temperature to 90°C, N 2After degassing for 30min, add 2,2'-azobisisobutylamidine dihydrochloride (V-50, 10wt%, 10ml), under N 2 Protected and reacted at 90°C for 24h to obtain PS spheres.

[0043] With 0.8g cetyltrimethylammonium bromide (CTAB), 29g H 2 O, 12 g of ethanol, and 1 ml of ammonia water were mixed to form a homogeneous solution, and 10 g of PS (~9%) was added dropwise under vigorous stirring at room temperature. After the dropwise ad...

Embodiment 2

[0052] The preparation method of the PH-stimulus-responsive intelligent nano container of the present invention, the steps are as follows:

[0053] Step 1, prepare mesoporous silica microspheres MCM-41, and vacuum-dry the obtained mesoporous silica microspheres; the preparation process of mesoporous silica microspheres MCM-41 is Step 1 in the above-mentioned Example 1.

[0054] Step 2, 200 mg of dried mesoporous silica microspheres and 80 ul of alkynyl-containing silane coupling agent APTS are dealcoholized in 10 ml of dried toluene; the alkynyl-containing silane coupling agent is prop- tert-butyl 2-yn-1-yl(3-(triethoxysilyl)propyl)carbamate. The dealcoholization reaction is carried out under nitrogen protection, wherein the mass ratio of mesoporous silica nanoparticles to the alkynyl-containing silane coupling agent is 2.5:1, and the concentration of the alkynyl-containing silane coupling agent in toluene is 8 μg / mL.

[0055] Step 3, preparation of 2-bromo-ethoxy-2-azido-et...

Embodiment 3

[0060] The preparation method of the PH-stimulus-responsive intelligent nano container of the present invention, the steps are as follows:

[0061] Step 1, prepare mesoporous silica microspheres MCM-41, and vacuum-dry the obtained mesoporous silica microspheres; the preparation process of mesoporous silica microspheres MCM-41 is Step 1 in the above-mentioned Example 1.

[0062] Step 2, 200mg of dried mesoporous silica microspheres and 90ul alkynyl-containing silane coupling agent APTS are dealcoholized in 15ml of dried toluene; the alkynyl-containing silane coupling agent is prop- tert-butyl 2-yn-1-yl(3-(triethoxysilyl)propyl)carbamate. The dealcoholization reaction is carried out under nitrogen protection, wherein the mass ratio of mesoporous silica nanoparticles to the alkynyl-containing silane coupling agent is 2.2:1, and the concentration of the alkynyl-containing silane coupling agent in toluene is 6 μg / mL.

[0063] Step 3, preparation of 2-bromo-ethoxy-2-azido-ethoxypr...

technical field

[0001] The invention belongs to the technical field of material science, in particular to a PH-stimulus responsive intelligent nano container and a preparation method thereof. Background technique

[0002] In the field of cell activity detection, because the pH value in the cell is not uniformly distributed, the pH value of the cytoplasm is about 7.2, and some organelles, such as lysosomes and endoplasmic reticulum, have an internal pH value of about 4.0 to 6.0 , showing weak acidity. Lysosomes contain more than 50 kinds of enzymes, which can be activated in the acidic environment of lysosomes to promote the degradation of proteins in cell metabolism. Once the pH gradient in the lysosome disappears, it is likely that the cell has a functional disorder. Therefore, detecting the change of pH in living cells is very meaningful for the study of cell function and its physiological and pathological processes. Although there have been many reports for monitoring a...

Examples

Embodiment 1

[0040] The preparation method of the PH-stimulus-responsive intelligent nano container of the present invention, the steps are as follows:

[0041] Step 1, preparing mesoporous silica microspheres MCM-41, and vacuum-drying the obtained mesoporous silica microspheres; the preparation process of mesoporous silica microspheres MCM-41 is as follows:

[0042] Dissolve 1.0g of acryloyloxyethyltrimethylammonium chloride (AETAC) in 390ml of deionized water, add 40g of styrene, stir mechanically at room temperature for 30min, then raise the temperature to 90°C, N 2After degassing for 30min, add 2,2'-azobisisobutylamidine dihydrochloride (V-50, 10wt%, 10ml), under N 2 Protected and reacted at 90°C for 24h to obtain PS spheres.

[0043] With 0.8g cetyltrimethylammonium bromide (CTAB), 29g H 2 O, 12 g of ethanol, and 1 ml of ammonia water were mixed to form a homogeneous solution, and 10 g of PS (~9%) was added dropwise under vigorous stirring at room temperature. After the dropwise ad...

Embodiment 2

[0052] The preparation method of the PH-stimulus-responsive intelligent nano container of the present invention, the steps are as follows:

[0053] Step 1, prepare mesoporous silica microspheres MCM-41, and vacuum-dry the obtained mesoporous silica microspheres; the preparation process of mesoporous silica microspheres MCM-41 is Step 1 in the above-mentioned Example 1.

[0054] Step 2, 200 mg of dried mesoporous silica microspheres and 80 ul of alkynyl-containing silane coupling agent APTS are dealcoholized in 10 ml of dried toluene; the alkynyl-containing silane coupling agent is prop- tert-butyl 2-yn-1-yl(3-(triethoxysilyl)propyl)carbamate. The dealcoholization reaction is carried out under nitrogen protection, wherein the mass ratio of mesoporous silica nanoparticles to the alkynyl-containing silane coupling agent is 2.5:1, and the concentration of the alkynyl-containing silane coupling agent in toluene is 8 μg / mL.

[0055] Step 3, preparation of 2-bromo-ethoxy-2-azido-et...

Embodiment 3

[0060] The preparation method of the PH-stimulus-responsive intelligent nano container of the present invention, the steps are as follows:

[0061] Step 1, prepare mesoporous silica microspheres MCM-41, and vacuum-dry the obtained mesoporous silica microspheres; the preparation process of mesoporous silica microspheres MCM-41 is Step 1 in the above-mentioned Example 1.

[0062] Step 2, 200mg of dried mesoporous silica microspheres and 90ul alkynyl-containing silane coupling agent APTS are dealcoholized in 15ml of dried toluene; the alkynyl-containing silane coupling agent is prop- tert-butyl 2-yn-1-yl(3-(triethoxysilyl)propyl)carbamate. The dealcoholization reaction is carried out under nitrogen protection, wherein the mass ratio of mesoporous silica nanoparticles to the alkynyl-containing silane coupling agent is 2.2:1, and the concentration of the alkynyl-containing silane coupling agent in toluene is 6 μg / mL.

[0063] Step 3, preparation of 2-bromo-ethoxy-2-azido-ethoxypr...

Images