CN109224074A - Collaboration enhances antitumor near infrared light response type nano composite material - Google Patents
Collaboration enhances antitumor near infrared light response type nano composite material Download PDFInfo
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- CN109224074A CN109224074A CN201811368707.2A CN201811368707A CN109224074A CN 109224074 A CN109224074 A CN 109224074A CN 201811368707 A CN201811368707 A CN 201811368707A CN 109224074 A CN109224074 A CN 109224074A
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- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/50—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates
- A61K47/51—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the non-active ingredient being a modifying agent
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Abstract
The invention discloses a kind of collaborations to enhance antitumor near infrared light response type NaYF4:Yb,Er‑NH2/ RBS/GO/BNN6 nanocomposite, is followed successively by NaYF from internal layer to outer layer4:Yb,Er‑NH2Layer, RBS layers of NO donor, GO layers, BNN6 layers of NO donor.NaYF prepared by the present invention4:Yb,Er‑NH2/ RBS/GO/BNN6 nanocomposite has good thermal stability and higher near-infrared responsiveness.NO release effectively can be triggered and be controlled by the adjustment of the switch of near infrared light laser, irradiation time and power density.NaYF4: Yb, Er and GO, NO donor RBS and BNN6 can play synergistic effect, greatly promote the response effect near infrared light, can significantly improve oncotherapy effect, present the antitumous effect of collaboration enhancing.
Description
Technical field
The present invention relates to a kind of collaborations to enhance antitumor near infrared light response type NaYF4:Yb,Er-NH2/RBS/GO/
BNN6 nanocomposite, metal nanometer material field.
Background technique
Nitric oxide (NO) is a kind of endogenous diatomic molecule, has played key in many physiology and pathological process
Adjustment effect, including vascular smooth muscle relaxation, immune response, neurotransmission, respiration, Apoptosis etc..The physiology of NO
Adjustment effect is largely dependent upon position, time and the dosage of NO release.NO can be stored and refer to by developing
Fixed place and the time release demand NO nanometer shipping platform have great importance (Acta PhySico-Chimica Sinica, 2017,33
(05): 903-917).
Current exogenous NO donor includes two alfin of azo, nitrosothiols, nitrobenzene and metal nitrosyl compounds etc..
It includes liposome, Nano particles of silicon dioxide, quantum dot, rear-earth-doped up-conversion luminescence nanomaterial that NO, which transports material,
(UCNPs), titanium dioxide, graphene oxide etc..
UCNPs is a kind of functional material that the anti-stoke that the photon of low energy can be converted into high-energy photons is luminous.
There is currently NO donor be mostly to discharge NO under the irradiation of ultraviolet light or visible light.But ultraviolet light has the group of difference
It knits penetration capacity and there is toxic action to healthy cell, these disadvantages limit most of NO donors further answering in vivo
With.Such as Zhang prepares surface and is coated with SiO2Core-shell structure UCNPs(UCNP@SiO2).UCNP@SiO2Surface is with just
Charge, the iron-sulfur cluster nitrosyl compound Lu Sen black salt Fe with negative electrical charge4S3(NO)7 -(RBS) electrostatic phase interaction can be passed through
With being adsorbed on UCNP@SiO2Surface.Due to the absorption spectrum of RBS have with the emission spectrum of UCNPs it is overlapping, near infrared light
Under the irradiation of 980nm, UCNPs converts the near infrared light of 980nm to the visible light of 550nm, and stimulation RBS controls release NO
(Small, 2012,8,3800).
Graphene oxide (GO) is the oxidation product of graphene, contains a large amount of hydroxyl, carboxyl and epoxy group.These contain
The introducing of oxygen activity group not only makes it possess good water-soluble and stability, but also GO can be made to be easier to modification and reach function
The effect of change.In addition to this, the two sides GO all has aromatic structure, and specific surface area is larger, can, hydrogen bond pi-conjugated by π-and dredge
The non-covalent bonds such as water effect are in conjunction with NO donor.Chen uses graphene oxide to pass through as the carrier of the light-operated release of NO for the first time
Graphene oxide and NO donor BNN6 are formed assembly by π-πconjugation.Graphene oxide absorbs near infrared light and turns electronics
NO light donor is moved on to, causes BNN6 to decompose and discharges NO(Nanoscale, 2015,7,20055).Sortino passes through covalent bond
Effect modifies NO donor NOP to the surface of GO using amido bond, forms a novel nanometer system GO-NOP1.GO-NOP1
It is very stable under dark condition with good water solubility, but generation (the Journal of of NO can be excited in the irradiation of visible light
Materials Chemistry B, 2016,4,5825).
Summary of the invention
Enhance antitumor near infrared light response type NaYF the present invention provides collaboration4:Yb,Er-NH2/RBS/GO/BNN6
Nanocomposite.
The technical scheme is that:
(1) by RBS([NH4][Fe4S3(NO)7]) it is slowly added into the NaYF of 0.1-10g/L4:Yb,Er-NH2Alcohol dispersion liquid
In, the RBS and NaYF4:Yb,Er-NH2Mass ratio be 0.5-5, react under room temperature for 24 hours, centrifugation, washing, it is dry after obtain
NaYF4:Yb,Er-NH2/ RBS nanocomposite.(2) by above-mentioned NaYF4:Yb,Er-NH2/ RBS nanocomposite slowly adds
Enter the HBP-NH to 1-100g/L2In aqueous solution, the NaYF4:Yb,Er-NH2/ RBS and HBP-NH2Mass ratio be 1-10,
It is reacted under room temperature for 24 hours, obtains NaYF after centrifugation, washing, drying4:Yb,Er-NH2/RBS/HBP-NH2Nanocomposite.(3)
GO is slowly added into the NaYF of 0.1-10g/L4:Yb,Er-NH2/RBS/HBP-NH2It is described in nanocomposite aqueous solution
NaYF4:Yb,Er-NH2/RBS/HBP-NH2Mass ratio with GO is 1-5, is reacted under room temperature for 24 hours, after centrifugation, washing, drying
To NaYF4:Yb,Er-NH2/ RBS/GO nanocomposite.(4) by the BNN6's of 0.1-10mol/L and 0.1-10mol/L
NaYF4:Yb,Er-NH2/ RBS/GO nanocomposite is uniformly mixed in ethanol, volume ratio 1:1, reacted under room temperature for 24 hours, from
NaYF is obtained after the heart, washing, drying4:Yb,Er-NH2/ RBS/GO/BNN6 nanocomposite.
Surface coats amine-terminated hyperbrancedization polyamide HBP-NH2NaYF4:Yb,Er-NH2Preparation method be existing skill
Art can refer in a kind of water solubility of Chinese invention patent CN201410701945.6 that inventor submitted on November 28th, 2014
Conversion nano particle and preparation method thereof.
The present invention has the advantages that the key that NO plays drug effect is how to realize the accurate and high-efficient controlled release of NO.Traditional
NO slow releasing pharmaceutical, NO concentration is uncontrollable, and drug side-effect is obvious, limits its clinical application.Nano material is NO payload
New approaches are provided with controlled release.NaYF prepared by the present invention4:Yb,Er-NH2/ RBS/GO/BNN6 nanocomposite has
Good thermal stability and higher near-infrared responsiveness.When NO release can be by switch, the irradiation of near infrared light laser
Between and the adjustment of power density effectively trigger and control, oncotherapy effect can be significantly improved.More crucial place is, this
Invention overcome be used alone GO/NO donor nanocomposite, UCNPs/NO donor nanocomposite less than NaYF4:
Yb, Er and GO, NO donor RBS and BNN6 can play synergistic effect, greatly promote the response effect near infrared light, Neng Gouxian
It writes and improves oncotherapy effect, present the antitumous effect of collaboration enhancing.
Specific embodiment
The invention will be further elucidated with reference to specific embodiments.
Embodiment 1:(1) by RBS([NH4][Fe4S3(NO)7]) it is slowly added into the NaYF of 1g/L4:Yb,Er-NH2Ethyl alcohol
In dispersion liquid, the RBS and NaYF4:Yb,Er-NH2Mass ratio be 0.5, react under room temperature for 24 hours, centrifugation, washing, it is dry after
Obtain NaYF4:Yb,Er-NH2/ RBS nanocomposite.(2) by above-mentioned NaYF4:Yb,Er-NH2/ RBS nanocomposite is slow
Slowly it is added to the HBP-NH of 1g/L2In aqueous solution, the NaYF4:Yb,Er-NH2/ RBS and HBP-NH2Mass ratio be 1, room temperature
Lower reaction for 24 hours, obtains NaYF after centrifugation, washing, drying4:Yb,Er-NH2/RBS/HBP-NH2Nanocomposite.(3) by GO
It is slowly added into the NaYF of 1g/L4:Yb,Er-NH2/RBS/HBP-NH2In nanocomposite aqueous solution, the NaYF4:Yb,
Er-NH2/RBS/HBP-NH2Mass ratio with GO is 1, is reacted under room temperature for 24 hours, obtains NaYF after centrifugation, washing, drying4:Yb,
Er-NH2/ RBS/GO nanocomposite.(4) by the NaYF of the BNN6 of 0.1mol/L and 0.1mol/L4:Yb,Er-NH2/RBS/
GO nanocomposite is uniformly mixed in ethanol, volume ratio 1:1, is reacted under room temperature for 24 hours, is obtained after centrifugation, washing, drying
NaYF4:Yb,Er-NH2/ RBS/GO/BNN6 nanocomposite.
Embodiment 2:(1) by RBS([NH4][Fe4S3(NO)7]) it is slowly added into the NaYF of 5g/L4:Yb,Er-NH2Ethyl alcohol
In dispersion liquid, the RBS and NaYF4:Yb,Er-NH2Mass ratio be 1, react under room temperature for 24 hours, centrifugation, washing, it is dry after
To NaYF4:Yb,Er-NH2/ RBS nanocomposite.(2) by above-mentioned NaYF4:Yb,Er-NH2/ RBS nanocomposite is slow
It is added to the HBP-NH of 10g/L2In aqueous solution, the NaYF4:Yb,Er-NH2/ RBS and HBP-NH2Mass ratio be 4, room temperature
Lower reaction for 24 hours, obtains NaYF after centrifugation, washing, drying4:Yb,Er-NH2/RBS/HBP-NH2Nanocomposite.(3) by GO
It is slowly added into the NaYF of 5g/L4:Yb,Er-NH2/RBS/HBP-NH2In nanocomposite aqueous solution, the NaYF4:Yb,
Er-NH2/RBS/HBP-NH2Mass ratio with GO is 2, is reacted under room temperature for 24 hours, obtains NaYF after centrifugation, washing, drying4:Yb,
Er-NH2/ RBS/GO nanocomposite.(4) by the NaYF of the BNN6 of 5mol/L and 5mol/L4:Yb,Er-NH2/ RBS/GO receives
Nano composite material is uniformly mixed in ethanol, volume ratio 1:1, is reacted under room temperature for 24 hours, obtains NaYF after centrifugation, washing, drying4:
Yb,Er-NH2/ RBS/GO/BNN6 nanocomposite.
Embodiment 3:(1) by RBS([NH4][Fe4S3(NO)7]) it is slowly added into the NaYF of 10g/L4:Yb,Er-NH2Ethyl alcohol
In dispersion liquid, the RBS and NaYF4:Yb,Er-NH2Mass ratio be 3, react under room temperature for 24 hours, centrifugation, washing, it is dry after
To NaYF4:Yb,Er-NH2/ RBS nanocomposite.(2) by above-mentioned NaYF4:Yb,Er-NH2/ RBS nanocomposite is slow
It is added to the HBP-NH of 50g/L2In aqueous solution, the NaYF4:Yb,Er-NH2/ RBS and HBP-NH2Mass ratio be 8, room temperature
Lower reaction for 24 hours, obtains NaYF after centrifugation, washing, drying4:Yb,Er-NH2/RBS/HBP-NH2Nanocomposite.(3) by GO
It is slowly added into the NaYF of 10g/L4:Yb,Er-NH2/RBS/HBP-NH2In nanocomposite aqueous solution, the NaYF4:Yb,
Er-NH2/RBS/HBP-NH2Mass ratio with GO is 5, is reacted under room temperature for 24 hours, obtains NaYF after centrifugation, washing, drying4:Yb,
Er-NH2/ RBS/GO nanocomposite.(4) by the NaYF of the BNN6 of 10mol/L and 10mol/L4:Yb,Er-NH2/RBS/GO
Nanocomposite is uniformly mixed in ethanol, volume ratio 1:1, is reacted under room temperature for 24 hours, is obtained after centrifugation, washing, drying
NaYF4:Yb,Er-NH2/ RBS/GO/BNN6 nanocomposite.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention.For those of ordinary skill in the art, may be used also on the basis of the above description
To make other variations or changes in different ways.Here all embodiments can not be exhaustive.It is all to belong to this hair
Bright technical solution changes and variations that derived from are still in the scope of protection of the present invention.
Claims (7)
1. a kind of collaboration enhances antitumor near infrared light response type nano composite material, which is characterized in that from internal layer to outer layer
It is followed successively by NaYF4:Yb,Er-NH2Layer, RBS layers of NO donor, GO layers, BNN6 layers of NO donor.
2. a kind of collaboration according to claim 1 enhances antitumor near infrared light response type nano composite material, special
Sign is, the NaYF4:Yb,Er-NH2Surface coats amine-terminated hyperbrancedization polyamide HBP-NH2。
3. a kind of collaboration according to claim 1 enhances antitumor near infrared light response type nano composite material, special
Sign is, the NaYF4:Yb,Er-NH2It is combined between RBS by electrostatic interaction.
4. a kind of collaboration according to claim 1 enhances antitumor near infrared light response type nano composite material, special
Sign is, passes through HBP-NH between the RBS and GO2Bonding.
5. a kind of collaboration according to claim 1 enhances antitumor near infrared light response type nano composite material, special
Sign is, is combined between the GO and BNN6 by π-π effect.
6. enhancing antitumor near infrared light response type nano composite material to a kind of collaboration described in 5 according to claim 1
Preparation method, which is characterized in that preparation step includes:
(1) by RBS([NH4][Fe4S3(NO)7]) it is slowly added into the NaYF of 0.1-10g/L4:Yb,Er-NH2Alcohol dispersion liquid
In, the RBS and NaYF4:Yb,Er-NH2Mass ratio be 0.5-5, react under room temperature for 24 hours, centrifugation, washing, it is dry after obtain
NaYF4:Yb,Er-NH2/ RBS nanocomposite；
(2) by above-mentioned NaYF4:Yb,Er-NH2/ RBS nanocomposite is slowly added into the HBP-NH of 1-100g/L2Aqueous solution
In, the NaYF4:Yb,Er-NH2/ RBS and HBP-NH2Mass ratio be 1-10, react under room temperature for 24 hours, it is centrifugation, washing, dry
After obtain NaYF4:Yb,Er-NH2/RBS/HBP-NH2Nanocomposite；
(3) GO is slowly added into the NaYF of 0.1-10g/L4:Yb,Er-NH2/RBS/HBP-NH2Nanocomposite aqueous solution
In, the NaYF4:Yb,Er-NH2/RBS/HBP-NH2Mass ratio with GO is 1-5, is reacted under room temperature for 24 hours, and centrifugation, is done washing
NaYF is obtained after dry4:Yb,Er-NH2/ RBS/GO nanocomposite；
(4) by the NaYF of the BNN6 of 0.1-10mol/L and 0.1-10mol/L4:Yb,Er-NH2/ RBS/GO nanocomposite exists
It is uniformly mixed, volume ratio 1:1, is reacted under room temperature for 24 hours in ethyl alcohol, obtain NaYF after centrifugation, washing, drying4:Yb,Er-NH2/
RBS/GO/BNN6 nanocomposite.
7. enhancing antitumor near infrared light response type NaYF by the collaboration that claim 6 preparation method obtains4:Yb,Er-NH2/
RBS/GO/BNN6 nanocomposite.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109745289A (en) * | 2019-03-06 | 2019-05-14 | 长春工业大学 | A kind of nitric oxide gas response liposome and its preparation method and application |
| CN109867797A (en) * | 2019-02-20 | 2019-06-11 | 青岛大学 | A kind of dendritic macromole compound and the preparation method and application thereof that near-infrared response is luminous |
| CN110960724A (en) * | 2019-12-31 | 2020-04-07 | 暨南大学 | Medicinal hydrogel and preparation method thereof |
| CN111281976A (en) * | 2020-03-31 | 2020-06-16 | 中国人民解放军陆军军医大学第一附属医院 | Preparation method and application of functionalized graphene targeted sterilization material with photo-thermal and chemotherapy synergistic effects |
| CN111743914A (en) * | 2020-07-14 | 2020-10-09 | 上海师范大学 | Exploring the influencing factors of the reaction of the nitroso-iron-sulfur cluster compound and the hydrogen peroxide |
-
2018
- 2018-11-16 CN CN201811368707.2A patent/CN109224074A/en not_active Withdrawn
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109867797A (en) * | 2019-02-20 | 2019-06-11 | 青岛大学 | A kind of dendritic macromole compound and the preparation method and application thereof that near-infrared response is luminous |
| CN109867797B (en) * | 2019-02-20 | 2021-07-06 | 青岛大学 | Near-infrared response luminous dendritic macromolecular compound and preparation method and application thereof |
| CN109745289A (en) * | 2019-03-06 | 2019-05-14 | 长春工业大学 | A kind of nitric oxide gas response liposome and its preparation method and application |
| CN109745289B (en) * | 2019-03-06 | 2021-02-05 | 长春工业大学 | Nitric oxide gas response liposome and preparation method and application thereof |
| CN110960724A (en) * | 2019-12-31 | 2020-04-07 | 暨南大学 | Medicinal hydrogel and preparation method thereof |
| CN110960724B (en) * | 2019-12-31 | 2022-02-15 | 暨南大学 | Medicinal hydrogel and preparation method thereof |
| CN111281976A (en) * | 2020-03-31 | 2020-06-16 | 中国人民解放军陆军军医大学第一附属医院 | Preparation method and application of functionalized graphene targeted sterilization material with photo-thermal and chemotherapy synergistic effects |
| CN111281976B (en) * | 2020-03-31 | 2022-04-22 | 中国人民解放军陆军军医大学第一附属医院 | Preparation method and application of functionalized graphene targeted sterilization material with photo-thermal and chemotherapy synergistic effects |
| CN111743914A (en) * | 2020-07-14 | 2020-10-09 | 上海师范大学 | Exploring the influencing factors of the reaction of the nitroso-iron-sulfur cluster compound and the hydrogen peroxide |
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Application publication date: 20190118 |