A multi-stage propulsion motor with sensing function and a preparation method thereof

Abstract

The application discloses a kind of multistage propulsion motor with sensing function and preparation method thereof, it is related to the preparation technical field of micro-nanomotor.The method comprises the following steps: substitution reaction is carried out to KH and 3-hydroxybenzyl alcohol, then polypropylene glycol is added, and lactic acid is added to prepare polymer PLA-NB-PPG;Dissolved in DCM, add peroxide, AgNO3, photoinitiator and spirooxazine, electrospinning is carried out, and nanofiber membrane is prepared;Ultraviolet irradiation treatment is carried out, alcohol dispersion is used, then solvent is volatilized under reduced pressure, and multistage propulsion motor with sensing function is prepared.The motor of the application has the characteristics of self-provided double power and sensing, can double sensing of enhanced raman signal and fluorescence while moving, that is, multistage propulsion and multiple sensing can be realized.The application solves the problem that existing motor type biosensor has insufficient power, sensing and movement action is split.

Description

Technical Field

[0001] This invention relates to the field of micro / nano motor fabrication technology, specifically to a multi-stage propulsion motor with sensing function and its fabrication method. Background Technology

[0002] In recent years, micro / nanomotors have shown great potential in the field of biosensing. Compared with other biosensors, such as electrochemical, mass-based, or optical biosensors, motor-based biosensors can achieve autonomous movement at the micro / nanoscale by converting other forms of energy into kinetic energy. This allows micromechanicals to achieve internal mixing within samples, using their movement speed and distance as sensing signals for in-situ detection of untreated samples without the need for cumbersome cleaning and separation steps. They have been gradually applied to the detection of biomolecules. The introduction of micro / nanomotors enables rapid, simple, sensitive, and visual detection of biomolecules, which has positive implications for the field of biosensing. Furthermore, after surface functionalization, micro / nanomotors, which inherently possess motion capabilities, can also effectively capture and separate target substances in complex biological media. However, current motor-based biosensors suffer from insufficient power and a disconnect between sensing and motion. Therefore, providing a multi-stage propulsion motor with sensing capabilities is of great significance. Summary of the Invention

[0003] To address the aforementioned technical problems, the present invention aims to provide a multi-stage propulsion motor with sensing function and its preparation method, thereby solving the problems of insufficient power and disconnect between sensing and motion in existing motor-type biosensors.

[0004] The technical solution of this invention to solve the above-mentioned technical problems is as follows: A method for manufacturing a multi-stage propulsion motor with sensing function is provided, comprising the following steps:

[0005] (1) KH and 3-hydroxybenzyl alcohol were subjected to a substitution reaction to obtain 3-hydroxypotassium benzyl alcohol. Then, sulfonated polypropylene glycol was added to carry out a bimolecular nucleophilic substitution reaction to obtain photosensitized polypropylene glycol. Lactic acid was then added to carry out a polymerization reaction to obtain the polymer polylactic acid-3-hydroxybenzyl alcohol-polypropylene glycol.

[0006] (2) Dissolve the polymer polylactic acid-3-hydroxybenzyl alcohol-polypropylene glycol obtained in step (1) in dichloromethane, add peroxide, AgNO3, photoinitiator and spiroxazine, stir evenly, and then perform electrospinning to obtain nanofiber membrane;

[0007] (3) The nanofiber membrane obtained in step (2) is subjected to ultraviolet irradiation for 6-12 hours, dispersed with alcohol, and then the solvent is evaporated under reduced pressure to obtain a multi-stage propulsion motor with sensing function.

[0008] Based on the above technical solution, the present invention can be further improved as follows:

[0009] Furthermore, in step (1), the mass ratio of KH, 3-hydroxybenzyl alcohol, sulfonated polypropylene glycol and lactic acid is 0.1-0.2:0.3-0.6:1.5-3:0.4-0.8.

[0010] Furthermore, in step (1), the sulfonated polypropylene glycol is p-toluenesulfonated polypropylene glycol.

[0011] Furthermore, in step (2), the procedure is carried out at room temperature and under no-light conditions.

[0012] Furthermore, in step (2), the mass ratio of the polymer polylactic acid-3-hydroxybenzyl alcohol-polypropylene glycol and dichloromethane is 10-30:100.

[0013] Furthermore, in step (2), the mass ratio of the polymer polylactic acid-3-hydroxybenzyl alcohol-polypropylene glycol, peroxide, AgNO3, photoinitiator and spiroxazine is 1:0.8-1.2:0.8-1.2:0.1-0.4:0.4-1.

[0014] Furthermore, in step (2), the peroxide is Na2O2 and / or K2O2.

[0015] Furthermore, in step (2), the photoinitiator is benzoyl peroxide.

[0016] Furthermore, in step (2), spiroxazine is 1,3,3-trimethylindolinenaphthospiroxazine.

[0017] Furthermore, in step (2), the mixture is stirred for 7-10 hours.

[0018] Furthermore, in step (2), the electrospinning conditions are: humidity 25-35%RH%, spinning receiving distance 10-20cm, spinning voltage 10-20kv, and microfluidic propulsion pump speed 0.1-0.5mL / h.

[0019] The present invention also provides a multi-stage propulsion motor with sensing function prepared by the above method.

[0020] The present invention has the following beneficial effects:

[0021] 1. This invention utilizes the principle that the UV-responsive polymer polylactic acid-m-hydroxybenzyl alcohol-polypropylene glycol (PLA-NB-PPG) undergoes molecular-level fracture upon absorbing sufficient UV irradiation energy. Using this polymer as the spinning solution for electrospinning, the main structure of a nanomotor is prepared by adjusting different spinning conditions. Further, a mixture of peroxides, namely sodium peroxide and / or potassium peroxide (Na2O2 and / or K2O2), a photoinitiator (BPO), silver nitrate (AgNO3), and spiroxazine, is added to electrospinnally prepare a sensing motor with multi-stage propulsion. The motor of this invention features autonomously provided dual power and sensing capabilities, enabling simultaneous sensing of enhanced Raman signals and fluorescence, thus achieving multi-stage propulsion and multiple sensing functions, realizing a new function in the field of motor-based biosensors.

[0022] 2. The motor matrix of this invention is prepared from a UV-responsive fracture polymer, obtained through crack propagation and growth under UV irradiation, resulting in relatively uniform dimensions. Under UV irradiation, AgNO3 inside the motor is reduced to Ag. The primary propulsion of the motor originates from the decomposition of Na2O2 and / or K2O2, simultaneously generating hydrogen peroxide. The secondary propulsion of the motor originates from the decomposition of hydrogen peroxide under Ag catalysis. Na2O2 and / or K2O2 and Ag are embedded in the fibers. The two-stage propulsion motor can induce local fluid convection and vortices. Local fluid convection and vortices enhance the sensing signals of Ag and spiroxazine. The sensing function of Ag is realized through enhanced Raman signal, and the fluorescence signal of spiroxazine is realized through an acidic environment. The movement of the motor can enhance the enrichment of Ag for the enhanced Raman signal, achieving positive feedback of motion to sensing.

[0023] 3. The multi-stage propulsion motor with sensing function provided by the present invention has dual propulsion power sources. The local fluid convection and vortex provided by it enrich the detected substance, making the enhanced Raman signal easy to detect. Attached Figure Description

[0024] Figure 1 TEM image of the motor obtained in Example 1;

[0025] Figure 2 This is a simulation diagram of the first-stage drive of the motor obtained in Example 1;

[0026] Figure 3 This is a simulation diagram of the two-stage drive of the motor prepared in Example 1. Detailed Implementation

[0027] The principles and features of the present invention are described below with reference to the accompanying drawings. The examples given are for illustrative purposes only and are not intended to limit the scope of the invention. Unless otherwise specified in the examples, conventional conditions or conditions recommended by the manufacturer should be followed. Reagents or instruments whose manufacturers are not specified are all commercially available products.

[0028] Example 1:

[0029] A multi-stage propulsion motor with sensing function is manufactured by means of the following steps:

[0030] (1) 100 mg of KH and 300 mg of 3-hydroxybenzyl alcohol were subjected to a substitution reaction to obtain 3-hydroxypotassium benzyl alcohol. Then, 1.8 g of p-toluenesulfonated polypropylene glycol was added to carry out a bimolecular nucleophilic substitution reaction to obtain photosensitized polypropylene glycol. Then, 500 mg of lactic acid was added to carry out a polymerization reaction to obtain polymer PLA-NB-PPG (polymer polylactic acid-3-hydroxybenzyl alcohol-polypropylene glycol).

[0031] (2) Under room temperature and light-free conditions, half the mass of 1g of polymer PLA-NB-PPG obtained in step (1) was dissolved in 10g of DCM, and then the remainder was dissolved. The dissolution process was stirred for 12h. Then, 1g of Na2O2 and K2O2, 1g of AgNO3, 0.2g of photoinitiator benzoyl peroxide and 0.5g of 1,3,3-trimethylindolinenaphthospiroxazine were added and stirred for 8h. Then, electrospinning was performed. The electrospinning conditions were: humidity 30%RH%, spinning receiving distance 15cm, spinning voltage 15kv, and microfluidic propulsion pump speed 0.2mL / h. After spinning, the product was stored in a vacuum drying oven to obtain a nanofiber membrane.

[0032] (3) The nanofiber membrane obtained in step (2) was subjected to ultraviolet irradiation for 10 hours. After irradiation, the broken fiber segments were dispersed with alcohol, and then the solvent was evaporated under reduced pressure to obtain a multi-stage propulsion motor with sensing function.

[0033] Example 2:

[0034] A multi-stage propulsion motor with sensing function is manufactured by means of the following steps:

[0035] (1) 150 mg of KH and 400 mg of 3-hydroxybenzyl alcohol were subjected to a substitution reaction to obtain 3-hydroxypotassium benzyl alcohol. Then, 1.5 g of p-toluenesulfonated polypropylene glycol was added to carry out a bimolecular nucleophilic substitution reaction to obtain photosensitized polypropylene glycol. Then, 400 mg of lactic acid was added to carry out a polymerization reaction to obtain the polymer PLA-NB-PPG.

[0036] (2) Under room temperature and light-free conditions, half the mass of 1g of polymer PLA-NB-PPG obtained in step (1) was dissolved in 5g of DCM, and then the remainder was dissolved. The dissolution process was stirred for 12h. Then, 0.8g of Na2O2 and K2O2, 0.8g of AgNO3, 0.1g of photoinitiator benzoyl peroxide and 0.4g of 1,3,3-trimethylindoline naphthospiroxazine were added and stirred for 7h. Then, electrospinning was performed. The electrospinning conditions were: humidity 25%RH%, spinning receiving distance 10cm, spinning voltage 10kv, and microfluidic propulsion pump speed 0.1mL / h. After spinning, the product was stored in a vacuum drying oven to obtain a nanofiber membrane.

[0037] (3) The nanofiber membrane obtained in step (2) was subjected to ultraviolet irradiation for 6 hours. After irradiation, the broken fiber segments were dispersed with alcohol, and then the solvent was evaporated under reduced pressure to obtain a multi-stage propulsion motor with sensing function.

[0038] Example 3:

[0039] A multi-stage propulsion motor with sensing function is manufactured by means of the following steps:

[0040] (1) 200 mg of KH and 600 mg of 3-hydroxybenzyl alcohol were subjected to a substitution reaction to obtain 3-hydroxypotassium benzyl alcohol. Then, 3 g of p-toluenesulfonated polypropylene glycol was added to carry out a bimolecular nucleophilic substitution reaction to obtain photosensitized polypropylene glycol. Then, 800 mg of lactic acid was added to carry out a polymerization reaction to obtain the polymer PLA-NB-PPG.

[0041] (2) Under room temperature and light-free conditions, half of the mass of 1g of polymer PLA-NB-PPG obtained in step (1) was dissolved in 8g of DCM, and then the remainder was dissolved. The dissolution process was stirred for 12h. Then, 1.2g of Na2O2, 1.2g of AgNO3, 0.4g of photoinitiator benzoyl peroxide and 1g of 1,3,3-trimethylindolinenaphthospiroxazine were added and stirred for 10h. Then, electrospinning was performed. The electrospinning conditions were: humidity 35%RH%, spinning receiving distance 20cm, spinning voltage 20kv, and microfluidic propulsion pump speed 0.5mL / h. After spinning, the product was stored in a vacuum drying oven to obtain a nanofiber membrane.

[0042] (3) The nanofiber membrane obtained in step (2) was subjected to ultraviolet irradiation for 12 hours. After irradiation, the broken fiber segments were dispersed with alcohol and then the solvent was evaporated under reduced pressure to obtain a multi-stage propulsion motor with sensing function.

[0043] Example 4:

[0044] A multi-stage propulsion motor with sensing function is manufactured by means of the following steps:

[0045] In step (1), KH is 150mg, and the rest is the same as in Example 1.

[0046] Example 5:

[0047] A multi-stage propulsion motor with sensing function is manufactured by means of the following steps:

[0048] In step (1), the amount of p-toluenesulfonated polypropylene glycol is 2.7g, and the rest is the same as in Example 1.

[0049] Example 6:

[0050] A multi-stage propulsion motor with sensing function is manufactured by means of the following steps:

[0051] In step (1), the lactic acid is 750 mg, and the rest is the same as in Example 1.

[0052] Example 7:

[0053] A multi-stage propulsion motor with sensing function is manufactured by means of the following steps:

[0054] In step (2), the mass ratio of polymer PLA-NB-PPG to DCM is 30:100, and the rest is the same as in Example 1.

[0055] Example 8:

[0056] A multi-stage propulsion motor with sensing function is manufactured by means of the following steps:

[0057] In step (2), 0.4 g of photoinitiator benzoyl peroxide and 1 g of 1,3,3-trimethylindolinenaphthospirazine were added, and the rest was the same as in Example 1.

[0058] Example 9:

[0059] A multi-stage propulsion motor with sensing function is manufactured by means of the following steps:

[0060] In step (2), the spinning voltage is 20kV, and the rest is the same as in Example 1.

[0061] Example 10:

[0062] A multi-stage propulsion motor with sensing function is manufactured by means of the following steps:

[0063] In step (2), the speed of the spinning microfluidic propulsion pump is 0.5 mL / h, and the rest is the same as in Example 1.

[0064] Test case

[0065] 1. The multi-stage propulsion motor with sensing function prepared in Example 1 was subjected to TEM testing. The results are shown in […]. Figure 1 .

[0066] Depend on Figure 1 It can be seen that after the multi-stage driven nanomotor is dispersed in an ethanol solution, the morphology of the composite nanostructure can be observed, which is ellipsoidal.

[0067] II. The multi-stage propulsion motor with sensing function prepared in Example 1 was simulated using COMSOL simulation software in an aqueous solution at room temperature, and the calculations for the first and second stages of propulsion were performed. The results are shown in [the table below]. Figure 2-3 (in Figure 2 (200nm).

[0068] Depend on Figure 2-3 It can be seen that the propulsion speed of the first-stage thrust is 3-5 μm / s; the propulsion speed of the second-stage thrust is 7-11 μm / s.

[0069] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for manufacturing a multi-stage propulsion motor with sensing function, characterized in that, Includes the following steps: (1) KH and 3-hydroxybenzyl alcohol were subjected to a substitution reaction to obtain 3-hydroxypotassium benzyl alcohol. Then, sulfonated polypropylene glycol was added to carry out a bimolecular nucleophilic substitution reaction to obtain photosensitized polypropylene glycol. Lactic acid was then added to carry out a polymerization reaction to obtain the polymer polylactic acid-3-hydroxybenzyl alcohol-polypropylene glycol. (2) Dissolve the polymer polylactic acid-3-hydroxybenzyl alcohol-polypropylene glycol obtained in step (1) in dichloromethane, add peroxide, AgNO3, photoinitiator and spiroxazine, stir evenly, and then perform electrospinning to obtain nanofiber membrane; (3) The nanofiber membrane obtained in step (2) is subjected to ultraviolet irradiation for 6-12 hours, and the motor matrix is ​​prepared based on the principle of ultraviolet response fracture polymer. The matrix is ​​dispersed with alcohol, and then the solvent is evaporated under reduced pressure to obtain a multi-stage propulsion motor with sensing function. In step (2), the peroxide is Na2O2 and / or K2O2.

2. The method for manufacturing a multi-stage propulsion motor with sensing function according to claim 1, characterized in that, In step (1), the mass ratio of KH, 3-hydroxybenzyl alcohol, sulfonated polypropylene glycol and lactic acid is 0.1-0.2:0.3-0.6:1.5-3:0.4-0.

8.

3. The method for manufacturing a multi-stage propulsion motor with sensing function according to claim 1 or 2, characterized in that, In step (1), the sulfonated polypropylene glycol is p-toluenesulfonated polypropylene glycol.

4. The method for manufacturing a multi-stage propulsion motor with sensing function according to claim 1, characterized in that, In step (2), the procedure is carried out at room temperature and in the absence of light.

5. The method for manufacturing a multi-stage propulsion motor with sensing function according to claim 1, characterized in that, In step (2), the mass ratio of the polymer polylactic acid-3-hydroxybenzyl alcohol-polypropylene glycol and dichloromethane is 10-30:

100.

6. The method for manufacturing a multi-stage propulsion motor with sensing function according to claim 1, characterized in that, In step (2), the mass ratio of the polymer polylactic acid-3-hydroxybenzyl alcohol-polypropylene glycol, peroxide, AgNO3, photoinitiator and spiroxazine is 1:0.8-1.2:0.8-1.2:0.1-0.4:0.4-1.

7. The method for manufacturing a multi-stage propulsion motor with sensing function according to claim 1 or 6, characterized in that, In step (2), the photoinitiator is benzoyl peroxide.

8. The method for manufacturing a multi-stage propulsion motor with sensing function according to claim 1 or 6, characterized in that, In step (2), spiroxazine is 1,3,3-trimethylindolinenaphthospiroxazine.

9. The method for manufacturing a multi-stage propulsion motor with sensing function according to claim 1, characterized in that, In step (2), the electrospinning conditions are: humidity 25-35%RH%, spinning receiving distance 10-20cm, spinning voltage 10-20kv, and microfluidic propulsion pump speed 0.1-0.5mL / h.

10. A multi-stage propulsion motor with sensing function prepared by the method of any one of claims 1-9.

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