CN114349961A

CN114349961A - CuTCPP @ PDA particle and preparation method and application thereof

Info

Publication number: CN114349961A
Application number: CN202111578612.5A
Authority: CN
Inventors: 杨苹; 刘鲁英; 陈江; 廖玉珍; 叶鹏; 戴胜; 刘鹏; 王致钘
Original assignee: Southwest Jiaotong University
Current assignee: Southwest Jiaotong University
Priority date: 2021-12-22
Filing date: 2021-12-22
Publication date: 2022-04-15
Anticipated expiration: 2041-12-22
Also published as: CN114349961B

Abstract

The invention discloses a CuTCPP @ PDA particle and a preparation method and application thereof, belonging to the technical field of materials, wherein the preparation method of the CuTCPP @ PDA particle mainly comprises the following steps: adding copper porphyrin (CuTCPP) and Dopamine (DA) into a solvent, stirring and dissolving in the dark at room temperature, then dropwise adding ammonia water with the concentration of 25-28 wt%, continuously stirring for 20-48 hours, centrifugally collecting particles, washing and drying to obtain the CuTCPP @ PDA particles. The invention realizes the doping of copper porphyrin into polydopamine particles in a weak base environment to obtain CuTCPP @ PDA particles with acid response, and the CuTCPP @ PDA particles have wide application prospect in drug transportation and/or drug release; the preparation method is simple and easy to implement, and the raw materials can adopt commercial products, so that the preparation method has wide practical application value.

Description

CuTCPP @ PDA particle and preparation method and application thereof

Technical Field

The invention relates to the technical field of materials, and particularly relates to CuTCPP @ PDA particles and a preparation method and application thereof.

Background

Porphyrins are a class of macrocyclic compounds formed by four pyrrole rings linked by methine bridges. The parent of the porphyrin is a porphine ring (shown as a chemical formula (a), protoporphyrin HTCPP), and a compound formed by replacing hydrogen atoms on four meso-position carbons (5, 10, 15, 20) and eight beta-position carbons (2, 3, 7, 8, 12, 13, 17, 18) on the ring by other substituents is porphyrin (shown as a chemical formula (b)); four nitrogen atoms at the center of the porphyrin ring can coordinate with metal ions, so that stable metalloporphyrin compounds (shown as chemical formula (c)) such as copper porphyrin (copper (II) tetracarboxyphenyl porphyrin, CuTCPP) and the like are formed.

Polydopamine (PDA) is a eumelanin-like substance synthesized by oxidizing dopamine hydrochloride, and the surface of a Polydopamine nanomaterial contains many functional groups, such as catechol, amine, imine, and the like, which provide covalent bonding sites for other materials.

At present, no research report of CuTCPP @ PDA particles, and a preparation method and application thereof is found in the prior art.

Disclosure of Invention

Aiming at the defects, the invention aims to provide the CuTCPP @ PDA particle and the preparation method and application thereof.

In order to achieve the purpose, the invention adopts the following technical scheme:

the invention provides a preparation method of CuTCPP @ PDA particles, which comprises the following steps: adding copper porphyrin (CuTCPP) and Dopamine (DA) into a solvent, stirring and dissolving in the dark at room temperature, then dropwise adding ammonia water with the concentration of 25-28 wt%, continuously stirring for 20-48 hours, centrifugally collecting particles, washing and drying to obtain CuTCPP @ PDA particles; wherein the mass ratio of copper porphyrin to dopamine is 5-10: 280-320; the mass-volume ratio of the copper porphyrin to the ammonia water is 5-10: 0.2-1.

Further, the mass ratio of the copper porphyrin to the dopamine is preferably 6-8: 290-310; more preferably 7.8: 300.

Further, the mass-to-volume ratio (mg/mL) of the copper porphyrin to the ammonia water is 6-8: 0.2-0.5; more preferably 7.8: 0.3.

Further, the solvent is one or two of deionized water and ethanol; preferably, the solvent is a mixed solvent consisting of ethanol and deionized water in a volume ratio of 3-5: 7-12; more preferably a mixed solvent consisting of ethanol and deionized water in a volume ratio of 4: 9.

The invention also provides the CuTCPP @ PDA particle prepared by the preparation method.

The invention also provides application of the CuTCPP @ PDA particles in drug transportation and/or drug release.

The invention also provides a drug transport carrier, which comprises the CuTCPP @ PDA particles.

In summary, the invention has the following advantages:

1. the CuTCPP @ PDA particle can be decomposed under an acidic condition, has excellent pH response behavior, infrared driving performance and a function of catalytically releasing nitric oxide, and has a wide application prospect in drug transportation and/or drug release.

2. The principle of the CuTCPP @ PDA particles of the present invention, which are decomposable under acidic conditions, having excellent pH response behavior, is as follows (as shown in fig. 1): porphyrins tend to aggregate in one-dimensional direction, polydopamine carries cationic charge due to partial protonation under acidic or neutral conditions, and porphyrin molecules with negative charges are assembled into a large number of J-aggregates through electrostatic interaction; under alkaline conditions, these polydopamine cations almost disappear, and there is no direct interaction force allowing the Tetracarboxylporphyrin (TCPP) molecules to assemble into a sufficient amount of J-aggregates. The J-aggregates, however, can be regenerated by protonation of the polydopamine, so that the CuTCPP @ PDA particles will decompose under acidic conditions.

3. The invention realizes the doping of copper porphyrin into polydopamine particles in a weak base environment to obtain CuTCPP @ PDA particles with acid response.

Drawings

FIG. 1 is a schematic diagram of the CuTCPP @ PDA particles of the present invention having an acid response;

FIG. 2 is an SEM image of a PDA particle, HTCPP @ PDA particle, and CuTCPP @ PDA particle of the present invention;

FIG. 3 is an EDS energy spectrum of CuTCPP @ PDA particles of the present invention;

FIG. 4 is a graph showing the results of a fluorescence response test of HTCPP @ PDA particles of the present invention;

FIG. 5 is a graph showing the results of dissolution testing of CuTCPP @ PDA particles in accordance with the present invention;

FIG. 6 is a graph showing the results of infrared driving of the PDA particles and CuTCPP @ PDA particles of the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.

Thus, the following detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

This example provides a method for preparing CuTCPP @ PDA particles, comprising the steps of: preparing 78mL of solvent by ethanol and deionized water according to the volume ratio of 4:9, adding 7.8mg of copper porphyrin CuTCPP and 300mg of Dopamine (DA), placing on a stirrer, and stirring at room temperature in a dark place until the solvent is dissolved; then 0.3mL of ammonia water (25 wt%) is added dropwise, and stirring is continued for 24 h; and centrifugally collecting particles at the rotating speed of 10000r/min, washing with deionized water, and drying to obtain CuTCPP @ PDA particles.

Example 2

This example provides a method for making CuTCPP @ PDA particles, which differs from example 1 only in that: the mass of Dopamine (DA) is adjusted to be 315mg, and the mass of copper porphyrin CuTCPP is adjusted to be 6 mg; the rest steps and parameters are the same.

Example 3

This example provides a method for making CuTCPP @ PDA particles, which differs from example 1 only in that: the mass of Dopamine (DA) is adjusted to 285mg, the mass of copper porphyrin CuTCPP is adjusted to 9mg, and the dosage of ammonia water (25 wt%) is adjusted to 0.5 mL; the rest steps and parameters are the same.

Comparative example 1

The embodiment provides a preparation method of PDA particles, which comprises the following steps: preparing 78mL of solvent from ethanol and deionized water in a volume ratio of 4:9, adding 300mg of Dopamine (DA), placing on a stirrer, and stirring at room temperature in a dark place until the solvent is dissolved; 0.3mL of ammonia water (25 wt%) is added dropwise, and stirring is continued for 24 h; and centrifugally collecting particles at the rotating speed of 10000r/min, washing with deionized water, and drying to obtain the PDA particles.

Comparative example 2

This example provides a method of making HTCPP @ PDA particles, comprising the steps of: preparing 78mL of solvent by ethanol and deionized water according to the volume ratio of 4:9, adding 7.8mg of protoporphyrin HTCPP and 300mg of Dopamine (DA), placing on a stirrer, and stirring at room temperature in a dark place until the solvent is dissolved; 0.3mL of ammonia water (25 wt%) is added dropwise, and stirring is continued for 24 h; and centrifugally collecting particles at a rotating speed of 10000r/min, washing with deionized water, and drying to obtain the HTCPP @ PDA particles.

Experimental example 1

In this example, the sample particles obtained in example 1(CuTCPP @ PDA particles), comparative example 1(PDA particles) and comparative example 2(HTCPP @ PDA particles) were subjected to scanning electron microscope photography. SEM results show that the three particles are microspherical in morphology and clear in surface profile of the microsphere, as shown in FIG. 2. The sample particles obtained in example 1 were subjected to EDS analysis using a scanning electron microscope: the presence of PDA and protoporphyrin or copper porphyrin is demonstrated by the EDS spectrum of C, N, O elements, and the presence of copper porphyrin can be confirmed by the EDS spectrum of Cu, which proves the successful incorporation of copper porphyrin into the particles, as shown in FIG. 3.

In this example, unless otherwise specified and specifically described, the experimental procedures and the instruments or reagents used therein may be those according to the conventional methods in the art and commercially available products, and the description thereof is not repeated.

Experimental example 2

In this example, the sample particles obtained in example 1(CuTCPP @ PDA particles), comparative example 1(PDA particles) and comparative example 2(HTCPP @ PDA particles) were placed on a transparent glass plate and photographed by a laser confocal microscope. The particles are irradiated by light sources with excitation wavelengths of 488nm and 561nm respectively, and shooting results show that both the PDA and the CuTCPP @ PDA particles do not have the fluorescence effect, but the HTCPP @ PDA particles have the fluorescence effect, and the test result of the HTCPP @ PDA particles is shown in FIG. 4.

Experimental example 3

In this example, the sample particles obtained in example 1(CuTCPP @ PDA particles), comparative example 1(PDA particles) and comparative example 2(HTCPP @ PDA particles) were dissolved in 50% glacial acetic acid, NaOH solution at pH 10 and deionized water, respectively, and only the CuTCPP @ PDA particles were completely dissolved in 50% glacial acetic acid, but the solutions were hardly dissolved in deionized water and NaOH solution at pH 10, while the PDA and HTCPP @ PDA particles were not dissolved in the three solutions, and the test results of the CuTCPP @ PDA particles are shown in FIG. 5.

Experimental example 4

In this example, the infrared driving experiment was carried out on the sample particles obtained in example 1(CuTCPP @ PDA particles) and comparative example 1(PDA particles) by the following procedure: dissolving the prepared CuTCPP @ PDA particles and Polydopamine (PDA) particles in RO water, irradiating the solution by using infrared rays, and observing under an optical microscope. As a result: the CuTCPP @ PDA particles retained the infrared drive of the Polydopamine (PDA) particles, and the results of the test are shown in fig. 6.

In conclusion, the invention realizes that the copper porphyrin is doped into the polydopamine particles in the weak base environment to obtain the CuTCPP @ PDA particles with acid response, and the CuTCPP @ PDA particles have wide application prospects in drug transportation and/or drug release; the preparation method is simple and easy to implement, and the raw materials can adopt commercial products, so that the preparation method has wide practical application value.

The foregoing is merely exemplary and illustrative of the present invention and it is within the purview of one skilled in the art to modify or supplement the embodiments described or to substitute similar ones without the exercise of inventive faculty, and still fall within the scope of the claims.

Claims

1. A preparation method of CuTCPP @ PDA particles is characterized by comprising the following steps: adding copper porphyrin (CuTCPP) and Dopamine (DA) into a solvent, stirring and dissolving in the dark at room temperature, then dropwise adding ammonia water with the concentration of 25-28 wt%, continuously stirring for 20-48 hours, centrifugally collecting particles, washing and drying to obtain CuTCPP @ PDA particles; wherein the mass ratio of copper porphyrin to dopamine is 5-10: 280-320; the mass-volume ratio of the copper porphyrin to the ammonia water is 5-10: 0.2-1.

2. The method for preparing CuTCPP @ PDA particles as claimed in claim 1, wherein the mass ratio of copper porphyrin to dopamine is 6-8: 290-310.

3. The method of making a CuTCPP @ PDA particle of claim 1 or 2, wherein the mass ratio of copper porphyrin to dopamine is 7.8: 0.3.

4. The method of making CuTCPP @ PDA particles as recited in claim 1, wherein the solvent is one or both of deionized water and ethanol.

5. The method for preparing CuTCPP @ PDA particles as claimed in claim 1 or 4, wherein the solvent is a mixed solvent composed of ethanol and deionized water in a volume ratio of 3-5: 7-12.

6. The method of making CuTCPP @ PDA particles as recited in claim 5, wherein the solvent is a mixed solvent consisting of ethanol and deionized water in a volume ratio of 4: 9.

7. A preparation method of CuTCPP @ PDA particles is characterized by being prepared by the preparation method of the CuTCPP @ PDA particles as described in any one of claims 1-6.

8. Use of the CuTCPP @ PDA particle of claim 7 for drug transport and/or drug release.

9. A drug delivery vehicle comprising the CuTCPP @ PDA particle of claim 7.