CN115093494B - Light-controlled supermolecule micromotor and preparation method thereof - Google Patents
Light-controlled supermolecule micromotor and preparation method thereof Download PDFInfo
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- CN115093494B CN115093494B CN202210691408.2A CN202210691408A CN115093494B CN 115093494 B CN115093494 B CN 115093494B CN 202210691408 A CN202210691408 A CN 202210691408A CN 115093494 B CN115093494 B CN 115093494B
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- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
- C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
- C08B37/0015—Inclusion compounds, i.e. host-guest compounds, e.g. polyrotaxanes
Abstract
The invention discloses a light-controlled supermolecule micromotor and a preparation method thereof, wherein supermolecule chemistry is used for preparing a light-driven micromotor, a novel method for connecting functional particles of the micromotor and a light-oriented shape movement mode are provided, the connection between Pt nano particles and silicon dioxide is realized by utilizing light-controlled isomerism of azobenzene molecules, and simultaneously, mesoporous silicon dioxide can load medicines so that the micromotor has the functions of cargo transportation and the like. The light-controlled motor can realize quick or slow release of the medicine. Meanwhile, the mesoporous silica can be replaced by other micron-sized functional particles to realize functions of biosensing, cargo transportation and the like.
Description
Technical Field
The invention belongs to the technical field of micro-nano devices, and particularly relates to a light-controlled supermolecule micromotor and a preparation method thereof.
Background
Micromotors (micromotors) were invented for the first time in 2004, and have attracted the interests of a plurality of scholars due to the characteristics of small volume, easy decomposition and the like, and different shapes and driving modes have been developed so far. In appearance, the material is mainly divided into spherical, rod-shaped, tubular and spiral shapes. And different driving forms can be adopted by micro motors with different shapes, including chemical driving (additional fuel), physical driving (acousto-optic electro-magnetic heat) and the like. Currently, research on micromotors is mainly focused on environmental remediation and medical treatment. Because the micro motor can move freely, the micro motor can be used as an adsorption carrier of heavy metal ions or other chemical pollutants in a microenvironment, and the enrichment efficiency of the pollutants is effectively improved. In the aspect of medical treatment, the nano-particles have the characteristics of small volume, easy decomposition, targeted transportation and the like, and can be used for drug delivery, sensing, sterilization, targeted removal of cancer cells and the like.
In supramolecular chemistry, cyclodextrins, as host macrocyclic molecules, can form 1. And the cis-trans isomerization of azobenzene can be realized by the irradiation of ultraviolet light with different wavelengths (as shown in figure 1), and trans-azobenzene is separated from the cyclodextrin cavity. The main structure of the prior light-driven micromotor is an asymmetric double-sided sphere, and most of substrates are TiO 2 Isophotosensitive material. As shown in FIG. 2, when illuminated, water molecules are preferentially present in TiO 2 The surface decomposition causes a large amount of hydrogen ions to be generated in the vicinity thereof, and electrons generated inside gradually move from the inside to the inert metal surface on the other side. And hydrogen ions are reduced to hydrogen gas on the surface of the inert metal, resulting in a decrease in ion concentration. This process creates ion concentration differences on the asymmetric micro-motor surface, which drives the micro-motor to move along the illumination direction.
Because the existing light-driven micromotor uses metal and photosensitive materials which are not easy to decompose, the micromotor is easy to poison human bodies or pollute the environment in the application process. Based on the motion mechanism of the current light-driven micromotor, special requirements are required on materials for preparing the micromotor, so that the use of other functional materials such as porous materials or hydrogel is limited, and the use range of the light-driven micromotor is narrowed.
Disclosure of Invention
The materials for current optically driven micromotors are limited to the use of photosensitive materials and further limit the functionality of the micromotors. The invention provides a micromotor combining supermolecule and mesoporous silica, which has the characteristics of supermolecule light control property and micromotor autonomous movement and functionality.
The invention discloses a novel light control micromotor by combining a micromotor with photo-isomerisable supermolecules from a light control mechanism. Because the light control module is a supermolecule, the light control module has no more requirements on the material of the micromotor, and materials with stronger functionality, such as porous nano particles or hydrogel, can be used.
In order to solve the technical problem, the invention adopts the following technical scheme:
a preparation method of a light control supermolecule micromotor comprises the following steps:
(1) Connecting electronegative sulfonated cyclodextrin to mesoporous silica nanoparticles with amino groups on the surface through electrostatic adsorption to obtain mesoporous silica coated by the sulfonated cyclodextrin;
(2) Adding chloroplatinic acid hexahydrate into deionized water, fully stirring, adding a mixed solution of sodium citrate and citric acid, reacting for half a minute, quickly adding sodium borohydride for reaction, cooling to room temperature, performing centrifugal separation, washing with water, and drying in a vacuum drying oven to obtain platinum nanoparticles;
(3) Soaking the platinum nanoparticles prepared in the step (2) in a DMSO solution of mercaptoazobenzene, stirring in the dark to connect mercaptoazobenzene with the platinum nanoparticles, then carrying out centrifugal separation and water washing, diluting the precipitate with deionized water into a dispersion liquid to obtain a mercaptoazobenzene @ platinum nanoparticle aqueous solution, and refrigerating at 4 ℃ in the dark for storage;
(4) And (2) putting the mercaptoazobenzene @ platinum nanoparticle aqueous solution prepared in the step (3) and the mesoporous silica coated by the sulfonated cyclodextrin prepared in the step (1) into a centrifuge tube, shaking and mixing the solution on a shaking table in a dark place, and connecting the platinum nanoparticles and the mesoporous silica through the interaction between the cyclodextrin and the azobenzene to obtain the light-controlled supermolecule micromotor.
Further, the preparation method of the sulfonated cyclodextrin coated mesoporous silica of step (1) is as follows: dispersing 5mg of amino mesoporous silica in 9 mL of aqueous solution with the pH value of 5-6, performing ultrasonic treatment for 1-2 hours, dissolving 2.3mg of sulfonated cyclodextrin in 1mL of deionized water to prepare a sulfonated cyclodextrin solution with the concentration of 1mM, dripping the sulfonated cyclodextrin solution into the solution, stirring for 12-24 hours, performing centrifugal separation, washing for 3 times by using clear water, and performing vacuum drying on the obtained precipitate for later use.
Further, in the step (2), the mass ratio of the chloroplatinic acid hexahydrate to the sodium borohydride is 1 to 1.3, and the mass ratio of the sodium citrate to the citric acid is 1.3 to 1.7.
Further, in the step (2), sodium borohydride is rapidly added to react at 70 ℃ for 1h.
Further, the preparation method of the platinum nanoparticles in the step (2) is as follows: weighing 5.18mg of chloroplatinic acid hexahydrate, adding the chloroplatinic acid hexahydrate into 50mL of deionized water, fully stirring, adding a mixed solution of 1.1 mg of sodium citrate and 0.6mg of citric acid, reacting for half minute, quickly adding 0.44mg of sodium borohydride, reacting at 70 ℃ for 1 hour, cooling to room temperature, carrying out centrifugal separation, washing with water for multiple times, and drying in a vacuum drying oven to obtain the platinum nanoparticles with the particle size of 50 nm.
Further, the mass concentration of the platinum nanoparticles in the step (3) is 0.04% -0.16%.
Further, the concentration of the mercaptoazobenzene DMSO solution was 1mM.
Further, the mass ratio of the mesoporous silica wrapped by the sulfonated cyclodextrin in the step (4) to the mercaptoazobenzene @ platinum nanoparticles is 1 to 1:2, and the mesoporous silica and the mercaptoazobenzene @ platinum nanoparticles are mixed for 12 to 24h under shaking.
The invention also provides a light control supermolecule micromotor prepared by the preparation method.
The invention has the beneficial effects that: the invention provides a novel method for connecting functional particles of a micromotor and an optical tropism shape movement mode. The invention uses supermolecule chemistry for preparing the optical drive micromotor, realizes the connection between Pt nano particles and silicon dioxide by utilizing the optical control isomerism of azobenzene molecules, and simultaneously, the mesoporous silicon dioxide can load medicines, so that the mesoporous silicon dioxide has the functions of cargo transportation and the like. The light-controlled motor can realize quick or slow release of the medicine. Meanwhile, the mesoporous silica can be replaced by other micron-sized functional particles to realize functions of biosensing, cargo transportation and the like.
Drawings
FIG. 1 is a schematic diagram of cis-trans isomerism of mercaptoazobenzene produced by ultraviolet irradiation of different wavelengths;
FIG. 2 is a transmission electron micrograph of the synthesized platinum nanoparticles;
FIG. 3 is a schematic diagram of the synthesis of mercaptoazobenzene;
FIG. 4 is a transmission electron microscope and infrared spectrum of platinum nanoparticles linked with mercaptoazobenzene;
FIG. 5 is a transmission electron micrograph of a synthetic micromotor and IR spectra of sulfonated cyclodextrin modified mesoporous silica and its coupling with azobenzene; wherein a is a transmission electron microscope image of a synthetic micromotor, b is mesoporous silicon dioxide modified by sulfonated cyclodextrin and infrared spectrum of the mesoporous silicon dioxide linked with azobenzene;
FIG. 6 is a schematic view of light control of azobenzene isomerization to stop the micro-motor;
FIG. 7 is a nuclear magnetic image of azobenzene after UV irradiation;
fig. 8 is a graph of the motion curve and the mean square displacement of the micro motor under different hydrogen peroxide concentrations, wherein a is the motion curve of the micro motor under different hydrogen peroxide concentrations, and b is the mean square displacement of the micro motor under different hydrogen peroxide concentrations.
Detailed Description
The present invention will be further described with reference to the following examples. It is to be understood that the following examples are illustrative only and are not intended to limit the scope of the invention, which is to be given numerous insubstantial modifications and adaptations by those skilled in the art based on the teachings set forth above.
Example 1
The preparation method of the light-controlled supramolecular micromotor in the embodiment is as follows:
(1) Sulfonated cyclodextrin (purchased from Sigma-Aldrich, the substitution degree of sodium sulfate salt is 12-15 mol/beta-CD mol, the molecular weight is calculated according to the substitution degree of 13 in the application) has excellent water solubility and high electronegativity, and simultaneously, the hydrophobic cavity of the cyclodextrin is maintained; connecting electronegative sulfonated cyclodextrin to mesoporous silica nanoparticles (purchased from Nanjing Xiancheng nano, and the average particle diameter is about 100 nm) with amino groups on the surface through electrostatic adsorption; the method comprises the following specific steps of dispersing 5mg of amino mesoporous silica in 9 mL of aqueous solution with the pH value of 5-6, carrying out ultrasonic treatment for 1 hour, dissolving 2.3mg of sulfonated cyclodextrin in 1mL of deionized water, preparing a sulfonated cyclodextrin solution with the concentration of 1mM, dripping the sulfonated cyclodextrin solution into the solution, stirring for 12 hours, carrying out centrifugal separation, washing for 3 times by using clear water, and carrying out vacuum drying on the obtained precipitate for later use.
(2) Preparing platinum nanoparticles: reduction of chloroplatinic acid with sodium borohydride, addition of 7.2mg of chloroplatinic acid hexahydrate (Sigma-Aldrich, ACS reagent) to 50mL of deionized water, stirring well, addition of a mixed solution of 1.1 mg of sodium citrate and 0.6mg of citric acid, reaction for half a minute, and rapid addition of 0.44mg of sodium borohydride (0.01 mol/dm) -3 Purchased from 16940-66-2, inc., yinakai science Co., ltd., beijing), reacted at 70 ℃ for 1 hour, and then cooledCooling to room temperature, and centrifugally separating to obtain the platinum nano particles with the particle size of 50 nm. A TEM image of the platinum nanoparticles is shown in fig. 2.
(3) Preparation of mercaptoazobenzene: the synthesis of mercaptoazobenzene is shown in FIG. 3. 1.98g of hydroxyazobenzene, 7.1ml (60 mmol) of dibromobutane and 1.12g of potassium hydroxide are first refluxed in 150ml of ethanol under nitrogen for 12 hours. After cooling to room temperature, the solvent was removed by rotary evaporator. The residue was suspended in dichloromethane (100 mL) and the solid was filtered. The dichloromethane was removed in vacuo and the crude product was purified by flash column chromatography to afford an intermediate product as a brown powder.
0.19g of the intermediate product, 0.22g of thiourea, was heated under reflux in 10ml of ethanol for 12h. After cooling to room temperature, 10ml of an aqueous solution containing 0.19g of potassium hydroxide were added, refluxed for 3h under nitrogen and cooled to room temperature. The mixture was adjusted to pH =1 with 1mol/L hydrochloric acid and extracted with 30ml of diethyl ether. The organics were washed with brine and dried over sodium sulfate. The solvent was removed by vacuum and the crude product was purified by flash column chromatography to give mercaptoazobenzene.
(4) And (3) soaking the platinum nanoparticles prepared in the step (2) in the DMSO solution of mercaptoazobenzene prepared in the step (3) overnight in the dark to connect azobenzene with the nanoparticles. The method comprises the following specific steps: and (3) soaking the platinum nanoparticles prepared in the step (2) in 10ml of DMSO solution with the concentration of 1mM mercaptoazobenzene, and stirring for 5 hours in a dark place to connect the mercaptoazobenzene with the nanoparticles. And then, centrifugally separating, washing with clear water for 3 times, diluting the precipitate into 2mL of dispersion with deionized water, and refrigerating at 4 ℃ in the dark for storage, thereby obtaining the mercaptoazobenzene @ platinum nanoparticle aqueous solution.
A TEM image of platinum nanoparticles linked to mercaptoazobenzene is shown in FIG. 4a, from which it can be seen that compared to FIG. 2, a layer of cyclic species appears around the Pt nanoparticles, and further infrared characterization of the platinum nanoparticles and mercaptoazobenzene @ platinum nanoparticles was found to be 1136 cm (see FIG. 4 b) -1 And 3300-3700 cm -1 An obvious azobenzene characteristic peak is formed, so that the successful preparation of the mercaptoazobenzene @ platinum nano particle is proved;
(5) The hydrosulfuryl prepared in the step (4)Putting the aqueous solution of the azobenzene @ platinum nanoparticles and the mesoporous silica coated with the sulfonated cyclodextrin obtained in the step (1) into a centrifuge tube, and carrying out light-shielding mixing oscillation on a shaking table for 12 hours, wherein the mass ratio of the mesoporous silica coated with the sulfonated cyclodextrin to the mercaptoazobenzene @ platinum nanoparticles is 1; platinum nanoparticles are connected with mesoporous silica through host-guest interaction between cyclodextrin and azobenzene, and the prepared mesoporous silica micromotor is shown in figure 5a. FIG. 5b shows the infrared spectrum of the sulfonated cyclodextrin modified mesoporous silica and its coupling with azobenzene, found to be 1136 cm -1 Has obvious characteristic azobenzene peak.
1. The motion process of the micro motor: adding the micromotor into the solution containing 2% 2 O 2 And 1% of surfactant, the micro-motor generates bubbles by catalyzing hydrogen peroxide through self platinum nano-particles so as to move freely. When 420nm ultraviolet light is irradiated, cis-azobenzene is isomerized into a trans form and dissociated from the cyclodextrin cavity, so that the platinum nanoparticles are separated from the mesoporous silica, the mesoporous silica is changed into brownian motion, and the mean square displacement of the motion is shown in fig. 8 b.
2. Testing the isomerization efficiency of mercaptoazobenzene
As shown in fig. 7, nuclear magnetism is used to test the H spectrum change after the azobenzene is irradiated by ultraviolet light, and the isomerization efficiency of mercaptoazobenzene is 92% by calculating the area of the nuclear magnetic peak, which proves that mercaptoazobenzene has better isomerization efficiency.
3. The movement speed of the micro motor is tested
The speed of movement of the micromotors was tested with Nanosight (Malvern NS 300). Fig. 8a shows a motion trajectory of a micro motor photographed by Nanosight, and the micro motor performs random brownian motion in pure water. When the fuel hydrogen peroxide is added, the movement of the micro motor is obviously accelerated. In order to quantify the movement speed of the micro motor, the mean square displacement is used for representing the micro motor under the condition of different hydrogen peroxide concentrations, as shown in fig. 8 b. As can be seen from fig. 8b, the speed of the micro motor is increasing with the increase of the hydrogen peroxide concentration.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (5)
1. A preparation method of a light-controlled supermolecule micromotor is characterized by comprising the following steps:
(1) Connecting electronegative sulfonated cyclodextrin to mesoporous silica nanoparticles with amino groups on the surface through electrostatic adsorption to obtain mesoporous silica coated by the sulfonated cyclodextrin;
(2) Adding chloroplatinic acid hexahydrate into deionized water, fully stirring, adding a mixed solution of sodium citrate and citric acid, reacting for half a minute, quickly adding sodium borohydride for reaction, cooling to room temperature, performing centrifugal separation, washing with water, and drying in a vacuum drying oven to obtain platinum nanoparticles;
(3) Soaking the platinum nanoparticles prepared in the step (2) in a DMSO solution of mercaptoazobenzene, stirring in the dark to connect mercaptoazobenzene with the platinum nanoparticles, then carrying out centrifugal separation and water washing, diluting the precipitate with deionized water into a dispersion liquid to obtain a mercaptoazobenzene @ platinum nanoparticle aqueous solution, and refrigerating at 4 ℃ in the dark for storage;
(4) Placing the mercaptoazobenzene @ platinum nanoparticle aqueous solution prepared in the step (3) and the mesoporous silica coated by the sulfonated cyclodextrin prepared in the step (1) into a centrifuge tube, shaking and mixing the solution on a shaking table in a dark place, and connecting the platinum nanoparticles and the mesoporous silica through the interaction between the cyclodextrin and the azobenzene to obtain the light-controlled supermolecule micromotor;
the preparation method of the mesoporous silica coated by the sulfonated cyclodextrin in the step (1) comprises the following steps: dispersing 5mg of amino mesoporous silica in 9 mL of aqueous solution with the pH value of 5-6, performing ultrasonic treatment for 1-2 hours to obtain an amino mesoporous silica solution, dissolving 2.3mg of sulfonated cyclodextrin in 1mL of deionized water to prepare a sulfonated cyclodextrin solution with the concentration of 1mM, dripping the sulfonated cyclodextrin solution into the amino mesoporous silica solution, stirring for 12-24 hours, then performing centrifugal separation, washing for 3 times with clear water, and performing vacuum drying on the obtained precipitate for later use;
the preparation method of the mercaptoazobenzene in the step (3) comprises the following steps: firstly, refluxing 1.98g of hydroxyazobenzene, 7.1mL of dibromobutane and 1.12g of potassium hydroxide in 150mL of ethanol under a nitrogen atmosphere for 12 hours, cooling to room temperature, removing the solvent by using a rotary evaporator, suspending the residue in 100 mL of dichloromethane, filtering the solid, removing the dichloromethane by using a vacuum method, and purifying the crude product by using flash column chromatography to obtain a brown powdery intermediate product; heating and refluxing 0.19g of intermediate product and 0.22g of thiourea in 10ml of ethanol for 12h, cooling to room temperature, adding 10ml of aqueous solution containing 0.19g of potassium hydroxide, refluxing for 3h under nitrogen, and cooling to room temperature; adjusting the pH of the obtained mixture to be =1 by using 1mol/L hydrochloric acid, extracting with 30ml of diethyl ether, washing an organic substance obtained by extraction with saline water, drying with sodium sulfate, vacuumizing to remove a solvent, and purifying a crude product by using flash column chromatography to obtain mercaptoazobenzene;
the mass concentration of the platinum nanoparticles in the step (3) is 0.04-0.16%; the concentration of the mercaptoazobenzene DMSO solution is 1mM;
the mass ratio of the mesoporous silica wrapped by the sulfonated cyclodextrin to the mercaptoazobenzene @ platinum nanoparticles in the step (4) is 1 to 1, and the mixture is shaken and mixed for 12 to 24h.
2. The method for preparing a light-controlling supramolecular micromotor according to claim 1, characterized in that: in the step (2), the mass ratio of the chloroplatinic acid hexahydrate to the sodium borohydride is 1 to 1.3, and the mass ratio of the sodium citrate to the citric acid is 1.
3. The method for preparing a light-controlling supramolecular micromotor according to claim 1, characterized in that: and (3) rapidly adding sodium borohydride into the mixture obtained in the step (2) to react at the temperature of 70 ℃ for 1h.
4. A method of preparing a light-controlling supramolecular micromotor as claimed in claim 3, characterized in that: the preparation method of the platinum nanoparticles in the step (2) comprises the following steps: weighing 5.18mg of chloroplatinic acid hexahydrate, adding the chloroplatinic acid hexahydrate into 50mL of deionized water, fully stirring, adding a mixed solution of 1.1 mg of sodium citrate and 0.6mg of citric acid, reacting for half minute, quickly adding 0.44mg of sodium borohydride, reacting at 70 ℃ for 1 hour, cooling to room temperature, carrying out centrifugal separation, washing with water for multiple times, and drying in a vacuum drying oven to obtain the platinum nanoparticles with the particle size of 50 nm.
5. A light-controlling supramolecular micromotor produced by the method of production according to any one of claims 1 to 4.
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