CN107625962A - A kind of two-dimensional nano piece optical-thermal conversion material of PEG modifications and its application - Google Patents
A kind of two-dimensional nano piece optical-thermal conversion material of PEG modifications and its application Download PDFInfo
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- CN107625962A CN107625962A CN201710655253.6A CN201710655253A CN107625962A CN 107625962 A CN107625962 A CN 107625962A CN 201710655253 A CN201710655253 A CN 201710655253A CN 107625962 A CN107625962 A CN 107625962A
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Abstract
The present invention relates to a kind of two-dimensional nano piece optical-thermal conversion material of PEG modifications, by tetra hydroxyanthraquinone and bivalent cupric ion Coordinate self-assembly, formed again through PEG modifications, a diameter of 500~800nm of nanometer sheet, wherein tetra hydroxyanthraquinone, bivalent cupric ion mole dosage ratio are 1.5~2：1.The two-dimensional nano piece of the present invention, has the higher absorption coefficient of light near infrared region, under near-infrared laser irradiation, has higher photothermal deformation ability, has expanded optical-thermal conversion material now, the photo-thermal therapy available for tumour.
Description
(1) technical field
The present invention relates to a kind of New Two Dimensional nanometer sheet optical-thermal conversion material and its application.
(2) background technology
In recent years, the tumor thermal therapy based on photothermal deformation nano material turns into emerging treatment of cancer focus, its
Principle is that optical-thermal conversion material can absorb near infrared light energy, converts light energy into too high heat energy, thin for Thermal killed tumour
Born of the same parents, play oncotherapy purpose.Its near infrared light absorbed, human body skin can be effectively passed through, deep tumor tissues is reached, is focus
The skylight at position.Meanwhile its illumination wavelength is adjustable, range of exposures is controllable, smaller to injury of human, and many biomaterial scholars cause
Power is in this new material of synthesis, it has also become the study hotspot in biologic applications.
It is well known that Jenner's particle has certain photothermal deformation effect.Such as gold nanorods, can by the light energy of absorption,
Cause and show that plasma resonance acts on, and convert light energy into heat energy, the photo-thermal therapy for tumour.Further study show that
The metal nanoparticle of hollow-core construction makes photo-thermal conversion efficiency more bright because it has unique surface plasma enhancement effect
It is aobvious.Surface plasma (Surface Plasmons, SPs) refers to the electronics and photon in free vibration existing for metal surface
Interact and the caused electronics dilatational wave propagated along metal surface (section), it can be excited by electronics or light wave, be entered
And strengthen periphery fluorescent emission and produce photothermal deformation effect.The metal nanoparticle of cavity structure is by its cavity structure institute shape
Into big absorption cross-section, therefore there is higher photothermal deformation effect, cancer cell can be effectively killed by high temperature, so as to reach
The purpose for the treatment of.But due to heavy metal toxicity problem, its clinic conversion is restricted.In addition, carbon-based optothermal material, such as carbon nanometer
Pipe, graphene, reproducibility graphene etc..Although with photothermal deformation effect, it is limited in that the absorption coefficient of light is relatively low, light
Thermal conversion efficiency is low, and preparation process and functionalization program are cumbersome.Organic compound, such as indocyanine green, although with certain light
Hot-cast socket ability, but its serious photobleaching, the photo-thermal therapy for tumour for causing it not stablize.
(3) content of the invention
The present invention relates to a kind of New Two Dimensional nanometer sheet photo-thermal with good photo-thermal conversion efficiency and photo and thermal stability
Transition material and its application.
The technical solution adopted by the present invention is：
Formed by tetra hydroxyanthraquinone and bivalent cupric ion Coordinate self-assembly, then through PEG modifications, the nanometer sheet planar dimension
For 500~800nm × 500~800nm, wherein the ratio between tetra hydroxyanthraquinone, bivalent cupric ion mole dosage is 1.5~2：1.
Cu (II) and tetra hydroxyanthraquinone carbonyl C=O and methoxyl group C-O are coordinated, and in parent-hydrophobic forces, pi accumulation
Power, under van der Waals interaction, metal-complexing active force collective effect, it is self-assembly of two-dimensional nano piece.
The present invention utilizes tetra hydroxyanthraquinone monomeric organic compound, is total to by the hydroxyl on its anthracene nucleus, carbonyl and copper ion
Coordination, forms a kind of two-dimensional nano piece, and it has a larger sectional area, the higher absorption coefficient of light, under near infrared light,
With good photo-thermal conversion efficiency and photo and thermal stability.Its photo-thermal conversion efficiency reaches 38.9%.
The two-dimensional nano piece can comprise the following steps：
(1) by tetra hydroxyanthraquinone solution and CuCl2Neutral solution (pH 7.4) mixes, and stirs 1hrs, obtains two-dimensional nano piece
Mixed liquor；
(2) mixed liquor for obtaining step (1), washed by centrifugation, neutral PBS, obtain pure two-dimensional nano piece, then
It is added dropwise in double amino-polyethylene glycol, stirs 12~24h, be then centrifuged for, obtains the two-dimensional nano piece of PEG modifications
Optical-thermal conversion material.
The ratio between the nanometer sheet and double amino-polyethylene glycol quality dosages are preferably 1：10.
Specific method can be as follows：1mg tetra hydroxyanthraquinone is weighed using balance, adds 40 μ L tetrahydrofurans (THF), then
Be diluted to 1mL using the aqueous solution, and add thereto containing etc. quality copper ion CuCl2(pH 7.4) solution, and stir strongly
After mixing 1hr, using the PBS solution of neutrality, wash, centrifuge, be resuspended, 3 times repeatedly.It is then dispersed in standby in PBS cushioning liquid.
By the two-dimensional nano piece of acquisition：Double amino-polyethylene glycol mixing (PEG- (NH2)2) mass ratio be 1:10 mixing are stayed overnight, and profit
Washed, centrifuged with the PBS of neutrality, is resuspended 3 times repeatedly, obtain the two-dimensional nano piece of PEG modifications.
Copper is trace element necessary to a variety of enzymes in participant's body, micro beneficial to human body.The present invention is based on four hydroxyls
Base anthraquinone belongs to anthracycline compound together, spatially with certain planar structure, and the carbonyl C=O of tetra hydroxyanthraquinone and
Methoxyl group C-O is coordinated with divalent metal copper ion Cu (II), and design has synthesized a kind of New Two Dimensional nanometer sheet photothermal deformation material
Material.Its synthetic operation is easy, and the carbonyl C=O and methoxyl group C-O of tetra hydroxyanthraquinone match somebody with somebody with divalent metal copper ion Cu (II)
Position, and under van der Waals interaction, pi accumulation power and coordination power, the self assembly in water and prepare nanoscale uniform two
Nanometer sheet is tieed up, and is modified using PEG, obtains that there is good aqueous solubility and the two-dimensional nano piece of biocompatibility.It possesses
Higher absorption coefficient, photo and thermal stability, and photothermal deformation ability, it has good potential applicability in clinical practice.
Two-dimensional nano piece of the present invention, possess higher absorption coefficient, photo and thermal stability, and photothermal deformation ability.It can use
In the photo-thermal therapy of tumour.
The invention further relates to described two-dimensional nano piece optical-thermal conversion material answering in tumor thermal therapy medicine is prepared
With.The two-dimensional nano piece is administered by different dosage, and this depends on cancer patient's clinical condition of early stage imaging diagnosis.This
The dosage and concentration of invention two-dimensional nano piece, it can be determined by clinician is customary.Therapeutic regimen depends on various factors, example
Such as the cancer cell of imaging, tissue or tumour are scattered or local, the health degree of patient, age etc..
Two-dimensional nano piece constructed by the present invention can be administered by method of administration known to three kinds, including intravenously administrable, abdominal cavity
Administration, and the regional delivery form being locally administered.
The beneficial effects are mainly as follows：The invention provides a kind of New Two Dimensional nanometer sheet photothermal deformation material
Material, has larger sectional area, the higher absorption coefficient of light, under near infrared light, has good photo-thermal conversion efficiency
With photo and thermal stability, its photo-thermal conversion efficiency reaches 38.9%, available for the photo-thermal therapy of tumour, has preferable application prospect.
(4) illustrate
Fig. 1 is the transmission electron microscope of two-dimensional nano piece；
Fig. 2 is the UV, visible light near-infrared absorption spectrum of two-dimensional nano piece；
Fig. 3 is the photothermal deformation curve of two-dimensional nano piece.
(5) embodiment
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in
This：
Embodiment 1：
The tetra hydroxyanthraquinone powder that 1mg is weighed using electronic balance is dissolved in and fills 40 μ L and go in tetrahydrofuran solution, so
After add 950 μ L deionized waters, after mixing, add 10mg/mL CuCl thereto2(pH 7.4, pH being adjusted with NaOH) 10 μ L,
And stir 1h.13000rpm/min, centrifugation, after being precipitated, neutral PBS solution washing is added, 13000rpm/min, is centrifuged,
3 times repeatedly, after be dispersed in it is standby in PBS.
By the two-dimensional nano piece of acquisition：Double amino-polyethylene glycol mixing (PEG- (NH2)2) according to mass ratio be 1:10 is mixed
Close overnight, and using neutral PBS washings, centrifugation, be resuspended 3 times repeatedly, obtain the two-dimensional nano piece of PEG modifications.
Embodiment 2：
Embodiment 1 prepares two-dimensional nano chip size about 500~800nm × 500~800nm, possesses higher absorption coefficient,
Photo and thermal stability, and photothermal deformation ability.Photo-thermal therapy available for tumour.
Table is carried out to two-dimensional nano piece using transmission electron microscope (TEM), ultraviolet-visible spectrophotometer (UV-Vis-NIR)
Sign, and the ramp case after the detection two-dimensional nano piece 808nm laser irradiations of Opto-thertnal detection device, specific test result are as follows：
(1) transmission electron microscope (TEM)
Transmission electron microscope represents the pattern and nano-scale of two-dimensional nano piece.As a result reference picture 1, the scale at 0.2 μm is represented
Under, distribution and the pattern of two-dimensional nano piece are detected, it illustrates two-dimensional nano piece size uniformity, consistent appearance.
(2) ultraviolet-visible-near infrared spectrometer (UV-Vis-NIR)
UV-visible-near infrared absorption, represent the characteristic spectrum of two-dimensional nano piece.As a result reference picture 2, two wieners
Rice piece in 600-1000nm there is higher absorption coefficient, its 500nm or so to have higher unimodal, its absorption with Cu ions
Unanimously.Proof goes out new two-dimensional nano piece by coordination.
(3) the photo-thermal curve of two-dimensional nano piece
As a result Fig. 3 is seen.As seen from the figure, two-dimensional nano piece is under 808nm laser irradiation, compared with PBS solution, two wieners
Rice piece is increased to 57.8 DEG C in 5min, shows that it has good photothermal deformation ability.
Claims (4)
1. a kind of two-dimensional nano piece optical-thermal conversion material of PEG modification, by tetra hydroxyanthraquinone and bivalent cupric ion Coordinate self-assembly,
Formed again through PEG modifications, the nanometer chip size is 500~800nm × 500~800nm, wherein tetra hydroxyanthraquinone, cupric
Ion mole dosage ratio is 1.5~2：1.
2. two-dimensional nano piece optical-thermal conversion material as claimed in claim 1, it is characterised in that the two-dimensional nano piece is by as follows
Method is made：
(1) by tetra hydroxyanthraquinone solution and CuCl2Neutral solution mixes, and obtains the mixed liquor of two-dimensional nano piece；
(2) mixed liquor for obtaining step (1), washed by centrifugation, neutral PBS, pure two-dimensional nano piece is obtained, then by it
It is added dropwise in double amino-polyethylene glycol, stirs 12~24h, be then centrifuged for, obtains the two-dimensional nano piece photo-thermal of PEG modifications
Transition material.
3. two-dimensional nano piece optical-thermal conversion material as claimed in claim 3, it is characterised in that the nanometer sheet and double amino-poly-
The ratio between quality of glycol dosage is 1：10.
4. the two-dimensional nano piece optical-thermal conversion material as described in one of claims 1 to 3 is in tumor thermal therapy medicine is prepared
Application.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109432423A (en) * | 2018-11-13 | 2019-03-08 | 福建医科大学孟超肝胆医院(福州市传染病医院) | A kind of photosensitive nanoparticle compound and its preparation method and application |
| WO2019148802A1 (en) * | 2018-01-30 | 2019-08-08 | 深圳大学 | Nano-titanium photothermal agent and preparation method and application thereof |
| CN111333855A (en) * | 2020-04-03 | 2020-06-26 | 华南师范大学 | 1, 5-dihydroxy anthraquinone copper coordination polymer/graphene compound and preparation and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104689315A (en) * | 2015-03-19 | 2015-06-10 | 吉林大学 | Chitosan loading copper complex type nano-composite photo-thermal agent and preparation method thereof |
-
2017
- 2017-08-03 CN CN201710655253.6A patent/CN107625962B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104689315A (en) * | 2015-03-19 | 2015-06-10 | 吉林大学 | Chitosan loading copper complex type nano-composite photo-thermal agent and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| H. DWAIN COBLE ET AL: ""CHELATE POLYMERS OF COPPER(II) WITH VARIOUS DIHYDROXYQUINOID LIGANDS"", 《J. INORG, NUCL. CHEM.》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019148802A1 (en) * | 2018-01-30 | 2019-08-08 | 深圳大学 | Nano-titanium photothermal agent and preparation method and application thereof |
| CN109432423A (en) * | 2018-11-13 | 2019-03-08 | 福建医科大学孟超肝胆医院(福州市传染病医院) | A kind of photosensitive nanoparticle compound and its preparation method and application |
| CN111333855A (en) * | 2020-04-03 | 2020-06-26 | 华南师范大学 | 1, 5-dihydroxy anthraquinone copper coordination polymer/graphene compound and preparation and application thereof |
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