CN105236466A - Nanometer material used for photothermal therapy and preparation method thereof - Google Patents

Nanometer material used for photothermal therapy and preparation method thereof Download PDF

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Publication number
CN105236466A
CN105236466A CN201510609744.8A CN201510609744A CN105236466A CN 105236466 A CN105236466 A CN 105236466A CN 201510609744 A CN201510609744 A CN 201510609744A CN 105236466 A CN105236466 A CN 105236466A
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photo
nano material
nanometer
thermal therapy
preparation
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汪乐余
崔家斌
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/12—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)

Abstract

The invention discloses a nanometer material applicable to photothermal therapy and a preparation method thereof. The material designed by the invention has extremely-high photothermal conversion efficiency. According to the invention, hydrophobic Cu7S4 nanocrystalline is obtained by thermal decomposition of a single precursor; and on the premise that the original structure of the material is maintained, the surface properties of the material are changed by coating of an amphiphilic polymer, and the material is converted into an aqueous phase so as to obtain a monodisperse flake-assembly nanometer material, a monodisperse rod-assembly nanometer material and a nanometer superlattice nanometer material are obtained. Under same conditions, photothermal conversion efficiencies of the monodisperse flake-assembly and monodisperse rod-assembly Cu7S4 nanometer particles are 48.62% and 56.32%, respectively; while the photothermal conversion efficiency of the Cu7S4 nanometer superlattice is strongest and stable under irradiation of near-infrared light with a wavelength of 808 nm, reaching 65.7%. The application of the nanometer material in in-vitro photothermal therapy of cancer cells shows that the nanometer material provided by the invention is expected to be a medicament of photothermal therapy, so widespread concerns can be caused in the fields of material science, nanometer science, biological medicine, etc.

Description

A kind of nano material for photo-thermal therapy and preparation method thereof
Technical field
The invention belongs to technical field of nanometer material preparation, particularly a kind of Cu with catch light thermal conversion efficiency 7s 4nano super-lattice, can be applied to photo-thermal therapy.
Technical background
Owing to being considered to a kind of not damaged, nuisanceless, high efficiency cancer therapy based on the photo-thermal ablation of near infrared nano material, the therefore design of near infrared photo-thermal nano material, synthesis and assembling cause to be paid close attention to widely.Up to now, be the heat kill overstrain improving photo-thermal conversion efficiency and strengthen Subcutaneous tumor, people explore the photo-thermal medicament in a large number with near infrared light intensity absorption.Comprise the research that gold nanoshell, gold nanorods, gold nanometer cage, the gold nano grain of layering and several nanostructures of hollow gold nanosphere have been used near infrared light heat cure.Although the nanostructure based on gold has the good prospect not causing the biologically inert of cellularstructure considerable change and clinical photo-thermal ablation, these materials light stability under long-term laser radiation is bad, and has potential long term toxicity effect.Comprise carbon nanotube, the carbon nanomaterial of Graphene has good photo and thermal stability, but make their monodispersed oxidising processs in water have impact on their photo-thermal effect.
The composition of nano material, pattern, finishing and assembling are the key factors improving photo-thermal conversion efficiency.Therefore, need the design nanostructure of rationality, make its photo-thermal effect under near infrared light reach maximization.Due to local surface plasma resonance effect, comprise MoS 2, WS 2not only have stronger absorption in near-infrared region at interior semiconductor nano material, and photo-thermal conversion efficiency is excellent, which results in and pay close attention to widely.Recently, Cu is comprised 9s 5, Cu 7.2s 4, Cu 2-xse is nanocrystalline at the chalkogenide of interior copper, its photo-thermal conversion efficiency is respectively 25.7% (980nm), 56.7% (980nm), 22% (808nm), causes special attention with its low price, low toxicity, the heat-staple advantage of light.It is reported, increase Cu 2-xthe size of S nano particle can strengthen photo-thermal conversion efficiency, and this illustrates the photo-thermal conversion efficiency that the operation of assemble nanometer crystalline substance will affect local surface plasma resonance effect and cause.On the other hand, the infringement of near infrared light to human body of 808nm is less, and oxyphorase and water very little to its absorption, can more in depth penetrate ill Organ and tissue, so 808nm is more suitable for interior therapeutic than the near infrared light of 980nm.Therefore, develop and there is high photo-thermal efficiency and the Cu of morphology controllable at 808nm place 2-xs nanostructure is the important need in biomedical applications field.
Summary of the invention
The present invention is the demand meeting biomedical applications field, a kind of Cu with catch light thermal conversion efficiency of special design 7s 4nano super-lattice, can be applied to photo-thermal therapy.
The present invention adopts the method for the single presoma of thermolysis, obtains hydrophobic Cu 7s 4nanocrystalline, under the prerequisite keeping material original structure, change its surface properties by coated amphipathic polymer, be translated into aqueous phase, obtain the nano material of monodispersed sheet, bar-shaped assembling and nano super-lattice three types, this material can be applicable to photo-thermal therapy.
The preparation method of the nano material for photo-thermal therapy of the present invention, its concrete steps are as follows:
A. the Dodecyl Mercaptan mixing of the thioacetamide of 4-6ml oleyl amine, 4-6ml octadecylene, 0-100mg and 0.05-0.4ml is also slowly stirred, at the Cu (S of 150-210 DEG C of hemostasis 10-20mg 2cNBut 2) presoma, keep 10-60min at 145-190 DEG C;
B., after reacting naturally cooling, take out reaction solution centrifugal, obtain hydrophobic Cu 7s 4nanocrystalline, be then distributed in chloroform;
C. be add PSI in the NaOH aqueous solution of 0.5-10mM to 10mL concentration oAmchloroform dispersion liquid and the hydrophobic Cu that obtains of step b 7s 4nanocrystalline chloroform dispersion liquid, wherein PSI oAmcontent is 20-100mg, hydrophobic Cu 7s 4nanocrystalline content is 2-10mg, ultrasonic disperse;
D. last stirring at 30-60 DEG C evaporates chloroform, and the centrifugal nano material that must be used for photo-thermal therapy, is distributed in water.
Described PSI oAmpreparation method be: under 50-70 DEG C of condition, 1.2-2.0g polysuccinimide is dissolved in 25-40mL tetrahydrofuran (THF), add 1.5-1.8mL oleic acid subsequently, mixture reacts 3-8h under 85-120 DEG C of condition, is cooled to room temperature, methanol extraction reaction product, namely centrifugation obtains PSI oAm; Polysuccinimide number-average molecular weight scope 5000-7500.
When not adding thioacetamide in step a, the nano material for photo-thermal therapy finally obtained is sheet.
In step a, thioacetamide add-on is 0-30mg, and when not comprising 0, the nano material for photo-thermal therapy finally obtained is bar-shaped.
In step a, thioacetamide add-on is 30-80mg, and when not comprising 30, the nano material for photo-thermal therapy finally obtained is superlattice.
Beneficial effect of the present invention: the present invention's synthesis obtains the Cu with catch light thermal conversion efficiency, remarkable photo and thermal stability and good biocompatibility 7s 4nanostructure.First the present invention obtains the hydrophobic Cu with different-shape 7s 4nanostructure, then under the prerequisite keeping original pattern and photo-thermal conversion efficiency, successfully transfers it to aqueous phase.Under the same conditions, the Cu of monodispersed sheet and bar-shaped assembling 7s 4the photo-thermal conversion efficiency of nano particle is respectively 48.62% and 56.32%, and Cu 7s 4the photo-thermal conversion efficiency of nano super-lattice under the near infrared light of 808nm is the strongest and stable, reaches 65.7%.The external photo-thermal therapy being applied to cancer cells shows that this invention promises to be photo-thermal therapy medicament, and this will cause in fields such as Materials science, nano science and biological medicines pays close attention to widely.
Accompanying drawing explanation
The nano material of the photo-thermal therapy of Fig. 1: embodiment 1-3 synthesis is dispersed in the Electronic Speculum figure of oil phase and aqueous phase respectively.
Fig. 2: optical power density is 1W/cm 2808nm near infrared light according under, the photothermal deformation curve when nano material concentration of photo-thermal therapy of embodiment 1-3 synthesis is 0.15mg/mL.
Fig. 3: optical power density is 1W/cm 2808nm near infrared light according under, when the nano material concentration of photo-thermal therapy of embodiment 1-3 synthesis is 0.15mg/mL, after the heating curve in 360s and 360s, remove the temperature lowering curve after illumination.
Fig. 4: example photo before and after the photothermal deformation curve of nano material of the photo-thermal therapy that embodiment 3 is synthesized and illumination, a, b are respectively the photothermal deformation curve changing nanocrystalline concentration and optical power density, c figure is the BUCT character in daylight lower glass plate, wherein UT scribbles the nano material of photo-thermal therapy that embodiment 3 is synthesized, d figure for the sheet glass described in c figure be 1W/cm in optical power density 2808nm near infrared light according to the photothermal image after 1min.
Fig. 5: the detection of photo-thermal ablation HeLa cell is 1W/cm in optical power density 2808nm near infrared light according to after 5min, add without material and (a, d), add oil phase nano material (b, e) and add nano material (c, HeLa cell optical photograph f) of photo-thermal therapy of embodiment 3 synthesis.
Embodiment
Embodiment 1
A. the mixing of the Dodecyl Mercaptan (DDT) of 6ml oleyl amine (OAM), 4ml octadecylene (ODE) and 0.08ml is also slowly stirred, 205 DEG C time, inject the Cu (S of 15mg 2cNBut 2) presoma, keep 10min at 190 DEG C;
B., after reacting naturally cooling, take out reaction solution centrifugal (15000 revs/min) 10min, obtain hydrophobic Cu 7s 4nanocrystalline, be then distributed in 1ml chloroform;
C. add in the 10mL10mMNaOH aqueous solution and comprise 30mgPSI oAmthe Cu hydrophobic with 1mg 7s 4nanocrystalline chloroform dispersion liquid, ultrasonic (500W, 6 minutes);
DEG C d.60 stir 2h at and evaporate chloroform, centrifugal (12000 revs/min) 10min obtains the nano material of light sheets heat cure, is re-dispersed in 2ml deionized water.
Embodiment 2
A. Dodecyl Mercaptan (DDT) mixing of the thioacetamide (TA) of 4ml oleyl amine (OAM), 6ml octadecylene (ODE), 13mg and 0.1ml is also slowly stirred, 160 DEG C time, inject the Cu (S of 15mg 2cNBut 2) presoma, keep 60min at 145 DEG C;
B., after reacting naturally cooling, take out reaction solution centrifugal (15000 revs/min) 10min, obtain hydrophobic Cu 7s 4nanocrystalline, be then distributed in 1ml chloroform;
C. add in the 10mL0.5mMNaOH aqueous solution and comprise 40mgPSI oAmthe Cu hydrophobic with 1mg 7s 4nanocrystalline chloroformic solution, ultrasonic (500W, 6 minutes);
DEG C d.60 stir 2h at and evaporate chloroform.Centrifugal (12000 revs/min) 10min obtains hydrophilic crystalline substance, obtains the nano material of bar-shaped photo-thermal therapy, is re-dispersed in 2ml deionized water.
Embodiment 3
A. Dodecyl Mercaptan (DDT) mixing of the thioacetamide (TA) of 6ml oleyl amine (OAM), 4ml octadecylene (ODE), 75mg and 0.4ml is also slowly stirred, 200 DEG C time, inject the Cu (S of 15mg 2cNBut 2) presoma, keep 60min at 190 DEG C.
B., after reacting naturally cooling, take out reaction solution centrifugal (15000 revs/min) 10min, obtain hydrophobic Cu 7s 4nanocrystalline, be then distributed in 1ml chloroform;
C. add in the 10mL0.5mMNaOH aqueous solution and comprise 30mgPSI oAmthe Cu hydrophobic with 2mg 7s 4nanocrystalline chloroformic solution, ultrasonic (500W, 6 minutes);
DEG C d.60 stir 2h at and evaporate chloroform, centrifugal (12000 revs/min) 10min obtains hydrophilic crystalline substance, obtains the nano material of superlattice photo-thermal therapy, is re-dispersed in 2ml deionized water.

Claims (5)

1. for a preparation method for the nano material of photo-thermal therapy, it is characterized in that, its concrete steps are as follows:
A. the Dodecyl Mercaptan mixing of the thioacetamide of 4-6ml oleyl amine, 4-6ml octadecylene, 0-100mg and 0.05-0.4ml is also slowly stirred, at the Cu (S of 150-210 DEG C of hemostasis 10-20mg 2cNBut 2) presoma, keep 10-60min at 145-190 DEG C;
B., after reacting naturally cooling, take out reaction solution centrifugal, obtain hydrophobic Cu 7s 4nanocrystalline, be then distributed in chloroform;
C. be add PSI in the NaOH aqueous solution of 0.5-10mM to 10mL concentration oAmchloroform dispersion liquid and the hydrophobic Cu that obtains of step b 7s 4nanocrystalline chloroform dispersion liquid, wherein PSI oAmcontent is 20-100mg, hydrophobic Cu 7s 4nanocrystalline content is 2-10mg, ultrasonic disperse;
D. last stirring at 30-60 DEG C evaporates chloroform, and the centrifugal nano material that must be used for photo-thermal therapy, is distributed in water.
2. the preparation method of a kind of nano material for photo-thermal therapy according to claim 1, is characterized in that, described PSI oAmpreparation method be: under 50-70 DEG C of condition, 1.2-2.0g polysuccinimide is dissolved in 25-40mL tetrahydrofuran (THF), add 1.5-1.8mL oleic acid subsequently, mixture reacts 3-8h under 85-120 DEG C of condition, is cooled to room temperature, methanol extraction reaction product, namely centrifugation obtains PSI oAm; Polysuccinimide number-average molecular weight scope 5000-7500.
3. the preparation method of a kind of nano material for photo-thermal therapy according to claim 1, is characterized in that, when not adding thioacetamide in step a, the nano material for photo-thermal therapy finally obtained is sheet.
4. the preparation method of a kind of nano material for photo-thermal therapy according to claim 1, is characterized in that, in step a, thioacetamide add-on is 0-30mg, and when not comprising 0, the nano material for photo-thermal therapy finally obtained is bar-shaped.
5. the preparation method of a kind of nano material for photo-thermal therapy according to claim 1, is characterized in that, in step a, thioacetamide add-on is 30-80mg, and when not comprising 30, the nano material for photo-thermal therapy finally obtained is superlattice.
CN201510609744.8A 2015-09-22 2015-09-22 Nanometer material used for photothermal therapy and preparation method thereof Pending CN105236466A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106433634A (en) * 2016-09-19 2017-02-22 武汉华思创新科技有限公司 Preparation method of monodisperse PbS quantum dot
CN107158411A (en) * 2017-03-31 2017-09-15 北京化工大学 It is a kind of to be imaged the lower photo-thermal of guidance and the multifunctional nanocomposites of drug synergism and preparation method thereof for CT
CN110498447A (en) * 2019-08-05 2019-11-26 河南师范大学 A kind of synthetic method of tennis shape molybdenum disulfide micro Nano material and its preparing the application in photo-thermal anticancer drug
CN112850779A (en) * 2021-03-12 2021-05-28 南京师范大学 Hollow Cu7S4Nano cubic structure and preparation method and application thereof
CN114436318A (en) * 2022-01-07 2022-05-06 安徽师范大学 Aqueous phase synthesis preparation of monodisperse Cu2-xMethod for preparing S nanocrystal

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106433634A (en) * 2016-09-19 2017-02-22 武汉华思创新科技有限公司 Preparation method of monodisperse PbS quantum dot
CN106433634B (en) * 2016-09-19 2018-10-12 武汉华思创新科技有限公司 A kind of preparation method of monodisperse pulmbous sulfide quantum dot
CN107158411A (en) * 2017-03-31 2017-09-15 北京化工大学 It is a kind of to be imaged the lower photo-thermal of guidance and the multifunctional nanocomposites of drug synergism and preparation method thereof for CT
CN110498447A (en) * 2019-08-05 2019-11-26 河南师范大学 A kind of synthetic method of tennis shape molybdenum disulfide micro Nano material and its preparing the application in photo-thermal anticancer drug
CN112850779A (en) * 2021-03-12 2021-05-28 南京师范大学 Hollow Cu7S4Nano cubic structure and preparation method and application thereof
CN114436318A (en) * 2022-01-07 2022-05-06 安徽师范大学 Aqueous phase synthesis preparation of monodisperse Cu2-xMethod for preparing S nanocrystal
CN114436318B (en) * 2022-01-07 2023-10-31 安徽师范大学 Aqueous phase synthesis preparation of monodisperse Cu 2-x S nanocrystalline method

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Application publication date: 20160113