CN108159438A - A kind of photoacoustic imaging contrast medium of cancer diagnosis and its preparation method and application - Google Patents
A kind of photoacoustic imaging contrast medium of cancer diagnosis and its preparation method and application Download PDFInfo
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- CN108159438A CN108159438A CN201810139470.4A CN201810139470A CN108159438A CN 108159438 A CN108159438 A CN 108159438A CN 201810139470 A CN201810139470 A CN 201810139470A CN 108159438 A CN108159438 A CN 108159438A
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- 206010028980 Neoplasm Diseases 0.000 title claims abstract description 33
- 239000002872 contrast media Substances 0.000 title claims abstract description 27
- 201000011510 cancer Diseases 0.000 title claims abstract description 24
- 238000003384 imaging method Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000003745 diagnosis Methods 0.000 title claims abstract description 16
- 229910009819 Ti3C2 Inorganic materials 0.000 claims abstract description 48
- 239000000463 material Substances 0.000 claims abstract description 46
- 239000010936 titanium Substances 0.000 claims abstract description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 30
- 239000007864 aqueous solution Substances 0.000 claims abstract description 26
- 239000000843 powder Substances 0.000 claims abstract description 17
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 14
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims abstract description 14
- 238000012986 modification Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 230000004048 modification Effects 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 12
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims abstract description 12
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910010293 ceramic material Inorganic materials 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 239000004411 aluminium Substances 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910009818 Ti3AlC2 Inorganic materials 0.000 claims abstract description 7
- 229910052786 argon Inorganic materials 0.000 claims abstract description 4
- 238000000498 ball milling Methods 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims abstract description 4
- 238000005245 sintering Methods 0.000 claims abstract description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract 6
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract 6
- IYMAXBFPHPZYIK-BQBZGAKWSA-N Arg-Gly-Asp Chemical compound NC(N)=NCCC[C@H](N)C(=O)NCC(=O)N[C@@H](CC(O)=O)C(O)=O IYMAXBFPHPZYIK-BQBZGAKWSA-N 0.000 claims abstract 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 235000019441 ethanol Nutrition 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- 229910003978 SiClx Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000000502 dialysis Methods 0.000 claims description 2
- 201000007270 liver cancer Diseases 0.000 claims description 2
- 208000014018 liver neoplasm Diseases 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 238000001727 in vivo Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 230000008685 targeting Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 2
- 238000013475 authorization Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 206010073071 hepatocellular carcinoma Diseases 0.000 description 2
- 238000001198 high resolution scanning electron microscopy Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000002626 targeted therapy Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- -1 Ethyl alcohol Chemical compound 0.000 description 1
- 241000699670 Mus sp. Species 0.000 description 1
- 229910019762 Nb4C3 Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910004472 Ta4C3 Inorganic materials 0.000 description 1
- 229910003077 Ti−O Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 238000011503 in vivo imaging Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 102000006495 integrins Human genes 0.000 description 1
- 108010044426 integrins Proteins 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000012686 silicon precursor Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000007920 subcutaneous administration Methods 0.000 description 1
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical class C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/22—Echographic preparations; Ultrasound imaging preparations ; Optoacoustic imaging preparations
Abstract
Photoacoustic imaging contrast medium the present invention provides a kind of cancer diagnosis and preparation method thereof, this method comprises the following steps：(1) titanium valve, aluminium powder and graphite powder are mixed and carries out ball milling, compacting, under conditions of argon gas is passed through, carried out high temperature sintering, obtain Ti3AlC2Ceramic material；(2) step (1) gains are broken into powder, are placed in hydrofluoric acid and react, after centrifuge washing, be placed in tetrapropylammonium hydroxide aqueous solution and be stirred to react, centrifuge, wash, obtain Ti3C2MXenes materials；(3) by Ti3C2MXenes materials aqueous solution is instilled in the mixed aqueous solution of CTAC and TEA, is reacted；TEOS is added, is reacted at 80 DEG C, centrifuges, wash, obtains the MXene nanometer sheets of mesopore silicon oxide package；(4) to step (3) gains carry out polyethylene glycol surface modification, then with rgd peptide carry out covalent bond to get.Gained contrast medium imaging effect of the invention is excellent.
Description
Technical field
The invention belongs to nanometer technology and cancer diagnosis technology fields, and in particular to a kind of photoacoustic imaging pair of cancer diagnosis
Than agent and its preparation method and application.
Background technology
In recent years, stratiform two-dimensional material is due to the in-depth study with unique property and by extensive, wherein with
It is in the majority to the research of graphene nanometer sheet and black phosphorus nanometer sheet.MXene be by Univ Drexel Yury Gogotsi and
A kind of novel transition metal carbide with two-dimensional layered structure that Michel W.Barsoum were developed in 2011 or
Person's nitride material has many properties similar to graphene, such as good electric conductivity, larger specific surface area and higher
Intensity.At present, it has been found that about 70 kinds of MXene materials, including Ti3C2、 Ti2C、V2C、Nb2C、Nb4C3、Ta4C3And Ti4N3
Deng.For many years, how those skilled in the art is preferably preparing MXene materials and how to develop MXene materials
Application potential has done many trials.
In terms of the technology of preparing improvement of MXene materials, the prior art has carried out following main research：
It is carried in the Chinese patent that Shanghai Silicate Inst., Chinese Academy of Sciences is 106220180 A of CN in application publication number
A kind of preparation method of two dimensional crystal MXene nano materials has been supplied, this method solve the shortcomings that conventional hf etching technology,
Conducive to large-scale promotion application.
Providing one kind in the Chinese patent that Sichuan University is 107522202 A of CN in application publication number avoids high temperature from adding
The technology of preparing of the MXene materials of hf etching is pressed and utilized, there is certain industrial applications prospect.
Univ Drexel provides one kind with more low cost manufacturing MXene materials in international monopoly WO/2017044262
The method of material.
Aspect is being improved to MXene materials, the prior art has carried out following main research：
Co., Ltd of Samsung provides one kind in United States Patent (USP) US20170088429 A1 and removes surface-functionalized group
MXene materials preparation method so that the bulk properties of MXene materials are more fully protruded.
One kind is provided in the Chinese patent that Harbin Institute of Technology is 107579235 A of CN in application publication number to be applied to
The preparation method of the oxidation Mxene/S compounds of lithium-sulphur cell positive electrode has very high specific volume based on the material that this method obtains
Amount and cyclical stability, can be used as lithium sulfur battery anode material.
A kind of Ti is provided in the Chinese patent that Shenzhen University is 107009054 A of CN in application publication number3C2Mxene gathers
Object composite wave-suction material is closed, which can absorb and emit electromagnetic wave, reduce secondary pollution of the electromagnetic wave for environment.
One kind is provided in the Chinese patent that Dalian University of Technology is 107029562 A of CN in application publication number to be based on
The composite nanometer filtering film of Mxene can be used for handling the heavy metal and organic solvent in waste water.
A kind of titanium carbide-poly- is provided in the Chinese patent that Shaanxi Tech Univ is CN106633051A in application publication number
The composite material of aniline provides a kind of rodlike polyaniline in Chinese patent of the application publication number for 106633050 A of CN
Loaded modified titanium carbide provides a kind of TiO in the Chinese patent for being 104529455 B of CN in Authorization Notice No.2/
MXene-Ti3C2Low temperature preparation method, application publication number be 106587064 A of CN Chinese patent in provide a kind of ammonia
The Ti of base3C2Nanocomposite.The respective performances of above-mentioned material are better than common Ti3C2Mxene, in lithium-ion electric
There is the application prospect of bigger in terms of pond, super capacitor and photocatalysis.
A kind of high-performance is provided in the Chinese patent that South China Science ＆ Engineering University is 106178979 A of CN in application publication number
Two-dimensional layer Ti3C2- MXene films, the material have water flux, higher selectivity, good mechanical performance and the stabilization of superelevation
Property.
A kind of oxide is provided in the Chinese patent that Zhejiang Polytechnical University is 106229488 A of CN in application publication number
Pillared MXene composite materials, the material can be used as lithium ion battery negative material.
Shaanxi Tech Univ is in Chinese patent that application publication number is 104549149 A of CN, application publication number CN
The two-dimensional layer available for processing potassium permanganate and hexavalent chromium is each provided in the Chinese patent of 104587947 A
MXene-Ti3C2。
Shaanxi Tech Univ is 104,495,918 104538597 B and CN of B, CN of CN in Authorization Notice No.
Graininess, flakes and cubic TiO are each provided in the Chinese patent of 104496461 B2/MXene-Ti3C2Nanometer is multiple
Condensation material, these materials improve single MXene-Ti3C2The various performances of powder.
Intel company provides in international monopoly WO/2017/171736 to be prepared using MXene for transistor collection
Into nano-cable.
Univ Drexel provides a kind of MXene composite woods containing urea in United States Patent (USP) US20160336088
Material.
Explanation as exemplified above, although MXene materials have been obtained for the attention of people and have carried out multidirectional improvement,
In terms of the field for being its application is mostly battery technology and membrane technology.According to the inventors knowledge, at present, there has been no by MXene materials
The report of photoacoustic imaging contrast medium of the material as cancer diagnosis.
Invention content
In view of the shortcomings of the prior art, one of the objects of the present invention is to provide a kind of comparisons of the photoacoustic imaging of cancer diagnosis
The preparation method of agent, described method includes following steps：
(1) titanium valve, aluminium powder and graphite powder are mixed and carries out ball milling, compacting, under conditions of argon gas is passed through, carry out high temperature burning
Knot, obtains Ti3AlC2Ceramic material；
(2) by Ti obtained by step (1)3AlC2Ceramic material is broken into powder, is placed in hydrofluoric acid and reacts, to reacting gains
After being centrifuged and being washed, be placed in tetrapropylammonium hydroxide aqueous solution and be stirred to react, then to reaction gains carry out from
The heart simultaneously washs, and obtains Ti3C2MXenes materials；
(3) by Ti3C2MXenes materials aqueous solution is instilled in the mixed aqueous solution of CTAC and TEA, is stirred reaction；So
Afterwards, TEOS is added, reaction is stirred at 80 DEG C, is centrifuged, washed after completion of the reaction, obtains mesopore silicon oxide package
MXene nanometer sheets Ti3C2@mMSNs；
(4) PEG surface modifications Ti is carried out to the MXene nanometer sheets of mesopore silicon oxide package obtained by step (3)3C2@
Then mMSNs-PEG carries out covalent bond to get to the photoacoustic imaging contrast medium Ti of the cancer diagnosis with RGD3C2@mMSNs-
RGD (reaction principle is as shown in Fig. 6).
Mesoporous silicon oxide is successfully coated on by the present invention by simple molten-gel formats with vertical in form
Ti3C2On MXenes so that resulting materials have regular mesoporous, excellent hydrophily and dispersibility and abundant surface base
Group.
The present invention by using CTAC and TEOS respectively as pore creating material and silicon precursor, successfully by mesoporous silicon oxide
It is coated on Ti3C2On MXenes.Principle based on the process is the Ti obtained by step (2) of the present invention3C2The surface of MXenes
Rich-OH groups, the present invention will be by that will be in that electropositive CTAC carries out electrostatical binding, then by adding in silicon source substance therewith
TEOS carries out aquation and forms self assembly with CTAC, then in situ generated meso-porous titanium dioxide silicon layer.
As shown in one of embodiment, by tem observation, the MXene of the mesopore silicon oxide package of present invention gained receives
Rice piece has regular mesoporous SiO 2 layer.Result is taken pictures by light and shade field TEM and SEM takes pictures result it is found that by dioxy
After SiClx cladding, Ti3C2Still in the core position of the MXene nanometer sheets of gained mesopore silicon oxide package, the plane of MXene is opened up
Structure is flutterred also to be preserved.
Result is taken pictures it is found that existing on resulting materials surface of the present invention a large amount of mesoporous by high-resolution SEM.Pass through
N2The attached thermoisopleth of absorption-desorption and graph of pore diameter distribution, it is known that, the MXene nanometer sheets of the mesopore silicon oxide package of present invention gained
With big specific surface area (772 m2/ g), high porosity (0.96cm3/ g) and regular aperture (3.1nm).
The MXene that X-ray EDS and X-ray XPS results further demonstrate mesopore silicon oxide package obtained by the present invention receives
The composition of rice piece.
The present invention is using RGD as the ligand of integrin.Specifically, RGD is covalently bound to the mesoporous of PEG modifications by the present invention
The MXene nanometer sheets of silicon oxide-wrapped so that the contrast medium of present invention gained can have tumor locus targeting, and
Good cancer target effect (Fig. 7) is demonstrated in vivo, the cancer target efficiency comparative of 4h after injection：RGD targeting groups：Non-target
To group=16.72%：11.13%, it was confirmed that the good hepatoma-targeting ability of the material system.In addition, the PEG of surface modification can
To prevent the contrast medium of the present invention is nonspecific from being combined with haemocyanin, internal aggregation is avoided, extends contrast medium in body
The half-life period of interior cycle.
As shown in figure 5, present invention gained contrast medium is to have outstanding PA values in the range of 650~1000nm in wavelength, together
When, the linear related (R of concentration of PA values and contrast medium2=0.96).In vivo experiment, PA values inject body also with contrast medium
The extension of interior time and be gradually increasing, until 24 hours whens, reach peak.It is real-time, sensitive that this shows that contrast medium of the present invention can be used for
With the imaging technique targeted therapy of accurate cancer and monitor the process for the treatment of.
As the optional embodiment of the present invention, in step (1), the molar ratio of the titanium valve, aluminium powder and graphite powder is
2:1:1；And/or the purity of the titanium valve is 99.5%, the purity of aluminium powder is 99.5%, and the purity of graphite powder is 99%；With/
Or, the titanium valve and aluminium powder are -325 mesh, the graphite powder is -300 mesh；And/or when carrying out the compacting, under 30MPa
It carries out；And/or it when carrying out high temperature sintering, is sintered 2 hours at 1500 DEG C.
Preferred embodiment as the present invention.In step (2), by Ti obtained by step (1)3AlC2Ceramic material is broken into powder, puts
In a concentration of 40% hydrofluoric acid, react 3 days at room temperature；And/or when carrying out the washing, carried out using water and ethyl alcohol；
And/or the weight fraction of tetrapropylammonium hydroxide is 25% in the tetrapropylammonium hydroxide aqueous solution；And/or it is placed in hydrogen-oxygen
When being stirred to react in change tetrapropyl ammonium aqueous solution, reaction temperature is room temperature, and the reaction time is 3 days.
The present inventor is had found by many experiments, and hydroxide tetrapropyl is being performed etching and added in using hydrofluoric acid
When ammonium is reacted, the reaction time is 3 days at room temperature, can significantly reduce gained Ti3C2Two-dimensional.
The present invention is for Ti3C2The weight ratio and TEOS and Ti of MXenes, CTAC and TEA3C2MXenes materials are water-soluble
Influence of the volume ratio of liquid to resulting materials microstructure is investigated, and the results are shown in Figure 3.
Preferably, in step (3), by Ti3C2MXenes materials aqueous solution is instilled in the mixed aqueous solution of CTAC and TEA,
When being stirred reaction, reaction temperature is room temperature, reaction time 1.5h；And/or when adding in TEOS reactions, the reaction time 1
~1.5h.
It is molten first with ethyl alcohol and hydrochloric acid when carrying out the washing in step (3) as the optional embodiment of the present invention
The mix reagent of liquid is washed, and recycles ethyl alcohol and deionized water washing；In the mix reagent of the ethyl alcohol and hydrochloric acid solution,
The volume ratio of ethyl alcohol and hydrochloric acid solution is 10:1；The hydrochloric acid solution is the hydrochloric acid solution that volume fraction is 37%.
Preferably, in step (4), PEG surfaces are carried out to the MXene nanometer sheets of mesopore silicon oxide package obtained by step (3)
During modification, used method is：The MXene nanometer sheets of mesopore silicon oxide package obtained by step (3) are scattered in ethyl alcohol, are dripped
After adding APTES, flow back 12 hours in 80 DEG C, after being washed using deionized water to gains, be dispersed in PBS, add
NHS-PEG2000-MAL reacts 24 hours in room temperature, to get the mesoporous oxidation of PEG surface modifications after gains are dialysed
The MXene nanometer sheets of silicon package.
Preferably, in step (4), when carrying out covalent bond with RGD, the mesopore silicon oxide of PEG surface modifications is wrapped up
MXene nanometer sheets are dissolved in PBS, add the RGD of 0.1mol, are stirred to react at room temperature 24 hours.
Another object of the present invention be to provide by the optoacoustic for cancer diagnosis that the above method is prepared into
As contrast medium.
It is also an object of the present invention to provide be used for using the photoacoustic imaging contrast medium of above-mentioned cancer diagnosis in preparation
Application in terms of the reagent of cancer diagnosis, the cancer include liver cancer.
Beneficial effects of the present invention：
1st, contrast medium of the invention has excellent tumor-targeting, in tumor imaging with outstanding real-time, spirit
Quick property and accuracy are so that it can in terms of for diagnosing tumor, imaging technique targeted therapy and real-time monitoring；
2nd, contrast medium of the invention can when it is injected intravenously dosage down to 15.6 μ g/ml (in terms of wherein Ti elements),
Still there is outstanding imaging effect.
Description of the drawings
Fig. 1 is the phenogram in the MXene nanometer sheet building-up processes of mesopore silicon oxide of the present invention package；Wherein, a and b are
Ti3C2SEM photograph of the ceramic material under different amplification scales；C is Ti3C2The TEM photos of ceramic material；D is mesoporous oxidation
The TEM photos of the MXene nanometer sheets of silicon package (interior scale is 20nm)；E is the MXene nanometer sheets of mesopore silicon oxide package
Horizontal and vertical state is taken pictures photo (interior scale be 50nm), and left-side images are the MXene nanometer sheets of mesopore silicon oxide package
Light field TEM photos, details in a play not acted out on stage, but told through dialogues of the intermediate image for the MXene nanometer sheets of mesopore silicon oxide corresponding with left-side images position package
TEM photos, SEM photograph of the image right for the MXene nanometer sheets of mesopore silicon oxide package；F is mesopore silicon oxide package
The high-resolution SEM photograph (interior scale is 50nm) of MXene nanometer sheets and corresponding chemical element component (O, C, Si, Ti) imaging
Photo (interior scale is 50nm)；
Fig. 2 is the MXene nanometer sheets chemical composition and structural characterization figure wrapped up mesopore silicon oxide, wherein, a X-ray
EDS test results, b be X-ray XPS test results, c N2The attached thermoisopleth of absorption-desorption, d are mesopore silicon oxide package
The pore-size distribution situation of MXene nanometer sheets；
Fig. 3 is Ti3C2, the usage amount of CTAC, TEA, TEOS and the MXene that is wrapped up for mesopore silicon oxide of reaction time
The influence result figure of nanometer sheet microstructure；
Fig. 4 is to 4 gained Ti of embodiment3C2The material characterization figure of@mMSNs-RGD；Wherein, a Ti3C2、Ti3C2@
MMSNs and Ti3C2The particle diameter distribution of@mMSNs-RGD is as a result, b is Ti3C2、Ti3C2@mMSNs and Ti3C2@mMSNs-RGD's
Zeta current potentials are as a result, c is Ti3C2、 Ti3C2@mMSNs and Ti3C2Ultravioletvisible absorption (UV-vis) collection of illustrative plates of@mMSNs-RGD,
D is Ti3C2Infrared absorption (FTIR) collection of illustrative plates of@mMSNs-RGD and RGD, e Ti3C2@mMSNs-RGD are dispersed in different water-soluble
UV-vis collection of illustrative plates in liquid concentration (80 μ g/ml, 64 μ g/ml, 51 μ g/ml, 40 μ g/ml, 32 μ g/ml and 26 μ g/ml), f be
Absorption intensity and cell characteristic length ratio (A/L) are normalized under different concentration of aqueous solution (same to e) at 808nm wavelength, is come with this
Extinction coefficient is acquired as 19.6Lg-1cm-1；
Fig. 5 is 4 gained Ti of embodiment3C2The in vitro and in vivo optoacoustic developed image of@mMSNs-RGD, wherein, a Ti3C2@
The optoacoustic development imaging schematic diagram of mMSNs-RGD, b Ti3C2@mMSNs-RGD solution is in various concentration (15.6 μ g/ml, 31.3
It is μ g/ml, 62.5 μ g/ml, 125 μ g/ml, 250 μ g/ml, related to Ti) under PA values, c Ti3C2@mMSNs-RGD solution exists
Photoacoustic imaging under various concentration (same to a)；D be after the different injections time (0h, 4h, 12h, for 24 hours, 48h) when tumor locus
PA values；E be after different injections the time (0h, 4h, 12h, for 24 hours, 48h) when tumor locus photoacoustic imaging；
Fig. 6 is the preparation process schematic diagram of contrast medium targeting modification of the present invention.
Fig. 7 is the internal distribution experiments result figure of contrast medium of the present invention, and it is good that experiment proves that the contrast medium of the present invention has
Cancer target ability.
Specific embodiment
The present invention is specifically described below by embodiment, it is necessary to which indicated herein is that following embodiment is only used
It is further detailed in the present invention, it is impossible to be interpreted as limiting the scope of the invention, which is skilled in technique
Personnel still fall within protection scope of the present invention according to some nonessential modifications and adaptations that foregoing invention content is made.
1 Ti of embodiment3AlC2The synthesis of MXenes
By titanium valve (99.5% (w/w) purity, -325 mesh), aluminium powder (99.5% (w/w) purity, -325 mesh) and graphite powder
(99.0% (w/w) purity, grain size are less than 48 μm, -300 mesh) is with molar ratio 2:1:1 ratio mixing, then carries out ball milling 10h
Later, cake is pressed under the pressure of 30MPa, then by the cake in stove, under conditions of argon gas is passed through, in 1500
It is fired 2 hours at DEG C, obtains Ti3AlC2Ceramic material.
By gained Ti3AlC2After ceramic material is ground, a concentration of 40% hydrofluoric acid that 10g powder is placed in 60ml is collected
In aqueous solution, the etching reaction of 3 days is carried out at room temperature, is collected by centrifugation and is washed using water and ethyl alcohol later, Ran Houfen
Dissipate the TPAOH (Tetrapropylammonium hydroxide, tetrapropylammonium hydroxide) in 50ml a concentration of 25% (w/w)
It is stirred at room temperature in aqueous solution 3 days；It is centrifuged and using the remaining TPAOH of water and ethyl alcohol washing removal, is obtained later
Ti3AlC2MXenes。
As shown in Figure 1, the Ti obtained by the present embodiment3AlC2MXenes has typical two-dimensional layer topological structure, and has
The dispersibility of height.
The synthesis of the MXene nanometer sheets of 2 mesopore silicon oxide of embodiment package
By CTAC (Cetanecyltrimethylammonium chloride) aqueous solution of 10g a concentration of 10% (w/w)
Stirring 10 minutes is premixed at room temperature with TEA (triethanolamine) aqueous solution of 0.2g a concentration of 10% (w/w), then
The Ti that the embodiment 1 of a concentration of 0.5mg/ml of 10ml obtains is added dropwise3AlC2It is small to stir 1.5 at room temperature for the aqueous solution of MXenes
When；Later, 150 μ l TEOS are added in, are stirred 1 hour at 80 DEG C；It is then centrifuged for collecting precipitation, and wash 3 times using ethyl alcohol.
In above-mentioned reaction process, CTAC, can be by using ethyl alcohol and 37% HYDROCHLORIC ACID MIXED SOLVENT (V as meso-hole structure guiding agentEthyl alcohol:
V37% hydrochloric acid=10:1) 3 cleanings wash out for 12 hours at 78 DEG C.Later, it is cleaned 3 times using ethyl alcohol and is washed with deionized 2
After secondary, gains are scattered in ethyl alcohol.Original position light field TEM and details in a play not acted out on stage, but told through dialogues TEM is carried out to resulting materials to take pictures and carry out
SEM takes pictures, and the results are shown in Figure 1.
As shown in Fig. 2, carry out X-ray EDS detections, it is seen that the characteristic peak of Si, this shows that mesoporous silicon oxide is present in
Ti3AlC2In MXenes nanometer sheets.X-ray XPS testing results further demonstrate the chemical composition of the present embodiment gains.
455.7th, the characteristic peak of 461.5 and 103.5eV is respectively referred to for Ti-C keys, Ti-O keys and Si-O keys.
As shown in Fig. 2, pass through the attached thermoisopleth of N2 absorption-desorptions and graph of pore diameter distribution, it is known that, the mesoporous oxygen of present invention gained
The MXene nanometer sheets of SiClx package have big specific surface area (772m2/ g), high porosity (0.96cm3/ g) and regular hole
Diameter (3.1nm).
Embodiment 3
On the basis of the scheme of embodiment 2, the present embodiment has also investigated different Ti3C2The weight of MXenes, CTAC and TEA
Amount ratio and TEOS and Ti3C2Influence of the volume ratio of MXenes material aqueous solutions for resulting materials microstructure, result is such as
Shown in Fig. 3.
Embodiment 4
2 gains of embodiment are scattered in the ethyl alcohol of 80ml, the APTES of 100 μ l is added dropwise after back flow reaction at 80 DEG C
12 hours, obtain the MXene nanometer sheets (Ti of amidized mesopore silicon oxide package3C2@mMSNs-NH2), utilize deionized water
After carrying out 2 washings, it is dispersed in the PBS solution of 25ml；Then 0.5mol NHS-PEG2000-MAL are added in room temperature
Lower stirring 24 hours obtains the MXene nanometer sheets (Ti of the mesopore silicon oxide package of PEG modifications3C2@mMSNs-PEG), with dialysis
Bag (3000Da) is dissolved in the PBS of 25ml after purification, and the RGD for adding 0.1mol is stirred 24 hours at room temperature, is collected by centrifugation
Precipitation, and be washed with deionized 3 times, obtain the MXene nanometer sheets (Ti for the mesopore silicon oxide package for being connected to RGD3C2@
mMSNs-RGD)。
As shown in figure 4, NHS-PEG2000-MAL and RGD have successfully been connected on Ti3C2@mMSNs-NH2On.DLS test knots
Fruit shows, Ti3C2、Ti3C2@mMSNs and Ti3C2The average hydraulic diameter of@mMSNs-RGD be respectively 91.7nm, 116.3nm and
152.9 nm.In addition, zeta current potentials have further demonstrated that the present embodiment is successfully realized to NH2, PEG and RGD grafting.UV-
Vis test results are shown at 400~600nm, Ti3C2@mMSNs compare Ti3C2There is stronger absorption, show that silica is realized
Successful cladding.FTIR collection of illustrative plates further demonstrates the successful grafting of RGD.
In terms of experiment in vivo, good cancer target effect (figure is demonstrated by the subcutaneous mice with tumor of SMMC-7721 first
7), after injection 4h cancer target efficiency comparative：RGD targeting groups：Non-targeted group=16.72%：11.13%, it was confirmed that the material
The good hepatoma-targeting ability of material system.
In terms of photoacoustic imaging, as shown in figure 5, the present invention gained contrast medium in the range of 650~1000nm have it is outstanding
Photoacoustic signal (PA) value, meanwhile, the concentration of PA values and contrast medium is linear related (R=0.96).In vivo experiment, PA values
The extension of time is injected in vivo also with contrast medium and is gradually increasing, until 24 hours whens reach peak；In corresponding in-vivo imaging
In ideograph, (15.6 μ g/ml) photoacoustic signal of tumor region can also be detected under the conditions of extremely low injection concentration, it was confirmed that
Its superior tumor imaging ability.
Claims (9)
1. the preparation method of the photoacoustic imaging contrast medium of a kind of cancer diagnosis, which is characterized in that described method includes following steps：
(1) titanium valve, aluminium powder and graphite powder are mixed and carry out ball milling, compacting, under conditions of argon gas is passed through, carry out high temperature sintering,
Obtain Ti3AlC2Ceramic material；
(2) by Ti obtained by step (1)3AlC2Ceramic material is broken into powder, is placed in hydrofluoric acid and reacts, and reaction gains are carried out
It after centrifuging and washing, is placed in tetrapropylammonium hydroxide aqueous solution and is stirred to react, then reaction gains are centrifuged simultaneously
Washing, obtains Ti3C2MXenes materials；
(3) by Ti3C2MXenes materials aqueous solution is instilled in the mixed aqueous solution of CTAC and TEA, is stirred reaction；Then, then
TEOS is added in, reaction is stirred at 80 DEG C, is centrifuged, washed after completion of the reaction, obtains the MXene of mesopore silicon oxide package
Nanometer sheet；
(4) polyethylene glycol (PEG) surface modification is carried out to the MXene nanometer sheets of mesopore silicon oxide package obtained by step (3), then
Covalent bond is carried out to get to the photoacoustic imaging contrast medium of the cancer diagnosis with rgd peptide.
2. preparation method according to claim 1, which is characterized in that in step (1), the titanium valve, aluminium powder and graphite powder
Molar ratio be 2:1:1；And/or the purity of the titanium valve is 99.5%, the purity of aluminium powder is 99.5%, the purity of graphite powder
It is 99%；And/or the titanium valve and aluminium powder are -325 mesh, the graphite powder is -300 mesh；And/or when carrying out the compacting,
It is carried out under 30MPa；And/or it when carrying out high temperature sintering, is sintered 2 hours at 1500 DEG C.
3. preparation method according to claim 1 or 2, which is characterized in that in step (2), by Ti obtained by step (1)3AlC2
Ceramic material is broken into powder, is placed in a concentration of 40% hydrofluoric acid, reacts 3 days at room temperature；And/or carry out the washing
When, it is carried out using water and ethyl alcohol；And/or in the tetrapropylammonium hydroxide aqueous solution tetrapropylammonium hydroxide weight fraction
It is 25%；And/or be placed in tetrapropylammonium hydroxide aqueous solution when being stirred to react, reaction temperature is room temperature, the reaction time 3
My god.
4. preparation method according to claim 3, which is characterized in that in step (3), the Ti3C2MXenes, CTAC and
The weight ratio of TEA is 5:(1~1.5):(0.02~0.04)；And/or the Ti3C2MXenes material aqueous solutions it is a concentration of
0.5g/ml；And/or in step (3), the TEOS and Ti3C2The volume ratio of MXenes material aqueous solutions is 150~200 μ l:
10ml。
5. according to the preparation method described in claim 1,2 or 4, which is characterized in that, will in step (3) in step (3)
Ti3C2MXenes materials aqueous solution is instilled in the mixed aqueous solution of CTAC and TEA, and when being stirred reaction, reaction temperature is room
Temperature, reaction time 1.5h；And/or when adding in TEOS reactions, reaction time 1h；It is first sharp and/or when carrying out the washing
It is washed with the mix reagent of ethyl alcohol and hydrochloric acid, recycles ethyl alcohol and deionized water washing, the mixing of the ethyl alcohol and hydrochloric acid
In reagent, the volume ratio of ethyl alcohol and hydrochloric acid is 10:1, the hydrochloric acid is the hydrochloric acid solution that volume fraction is 37%.
6. preparation method according to claim 5, which is characterized in that in step (4), to oxidation mesoporous obtained by step (3)
When the MXene nanometer sheets of silicon package carry out polyethylene glycol surface modification, used method is：By oxygen mesoporous obtained by step (3)
The MXene nanometer sheets of SiClx package are scattered in ethyl alcohol, after APTES is added dropwise, is flowed back 12 hours in 80 DEG C, are utilized deionized water pair
It after gains are washed, is dispersed in PBS, adds NHS-PEG2000-MAL and reacted in room temperature 24 hours, by gains
To get the MXene nanometer sheets of the mesopore silicon oxide package of PEG modifications after dialysis.
7. preparation method according to claim 6, which is characterized in that, will when carrying out covalent bond with RGD in step (4)
The MXene nanometer sheets of mesopore silicon oxide package after PEG modifications are dissolved in PBS, are added the RGD of 0.1mol, are stirred at room temperature
Mix reaction 24 hours.
8. the photoacoustic imaging contrast medium for cancer diagnosis being prepared by any one of claim 1~7 preparation method.
9. the photoacoustic imaging contrast medium of cancer diagnosis according to any one of claims 8 answering in terms of the reagent for cancer diagnosis is prepared
With the cancer includes liver cancer.
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| CN110590366A (en) * | 2019-10-14 | 2019-12-20 | 陕西科技大学 | Preparation method of porous MXene material |
| CN110655080A (en) * | 2019-10-25 | 2020-01-07 | 山东大学 | Non-oxidation Ti with function of selectively killing cancer cells3C2Quantum dot and preparation method and application thereof |
| CN113456837A (en) * | 2021-07-14 | 2021-10-01 | 山西医科大学 | MXene @ BSA nano diagnosis and treatment agent with controllable size and preparation and application thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108987126A (en) * | 2018-09-28 | 2018-12-11 | 大连理工大学 | A kind of Ti3C2/ Ni combination electrode material and preparation method thereof |
| CN108987126B (en) * | 2018-09-28 | 2019-12-17 | 大连理工大学 | Ti3C2/Ni composite electrode material and preparation method thereof |
| CN110590366A (en) * | 2019-10-14 | 2019-12-20 | 陕西科技大学 | Preparation method of porous MXene material |
| CN110590366B (en) * | 2019-10-14 | 2022-03-25 | 陕西科技大学 | Preparation method of porous MXene material |
| CN110655080A (en) * | 2019-10-25 | 2020-01-07 | 山东大学 | Non-oxidation Ti with function of selectively killing cancer cells3C2Quantum dot and preparation method and application thereof |
| CN110655080B (en) * | 2019-10-25 | 2022-08-05 | 山东大学 | Non-oxidation Ti with function of selectively killing cancer cells 3 C 2 Quantum dot and preparation method and application thereof |
| CN113456837A (en) * | 2021-07-14 | 2021-10-01 | 山西医科大学 | MXene @ BSA nano diagnosis and treatment agent with controllable size and preparation and application thereof |
| CN113456837B (en) * | 2021-07-14 | 2022-12-02 | 山西医科大学 | MXene @ BSA nano diagnosis and treatment agent with controllable size and preparation and application thereof |
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