CN111484517A - Russian nesting doll type gold nanorod composite system loaded with novel mercapto nitrogen heterocyclic silicon (IV) phthalocyanine complex - Google Patents
Russian nesting doll type gold nanorod composite system loaded with novel mercapto nitrogen heterocyclic silicon (IV) phthalocyanine complex Download PDFInfo
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- CN111484517A CN111484517A CN202010362498.1A CN202010362498A CN111484517A CN 111484517 A CN111484517 A CN 111484517A CN 202010362498 A CN202010362498 A CN 202010362498A CN 111484517 A CN111484517 A CN 111484517A
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- phthalocyanine
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- hydroxyphenyl
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 75
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims description 19
- RWMKKWXZFRMVPB-UHFFFAOYSA-N silicon(4+) Chemical compound [Si+4] RWMKKWXZFRMVPB-UHFFFAOYSA-N 0.000 title claims description 18
- 125000000623 heterocyclic group Chemical group 0.000 title claims description 9
- ASZXGHPTTZYFFA-UHFFFAOYSA-N S[N] Chemical compound S[N] ASZXGHPTTZYFFA-UHFFFAOYSA-N 0.000 title claims description 7
- -1 bis- (1- (4-hydroxyphenyl) -5-mercapto-tetrazole) silicon (IV) Chemical compound 0.000 claims abstract description 21
- 239000010931 gold Substances 0.000 claims abstract description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052737 gold Inorganic materials 0.000 claims abstract description 20
- 241000894006 Bacteria Species 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 229940079593 drug Drugs 0.000 claims abstract description 9
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- BUMGIEFFCMBQDG-UHFFFAOYSA-N dichlorosilicon Chemical compound Cl[Si]Cl BUMGIEFFCMBQDG-UHFFFAOYSA-N 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
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- 238000003756 stirring Methods 0.000 claims description 13
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- JACPFCQFVIAGDN-UHFFFAOYSA-M sipc iv Chemical class [OH-].[Si+4].CN(C)CCC[Si](C)(C)[O-].C=1C=CC=C(C(N=C2[N-]C(C3=CC=CC=C32)=N2)=N3)C=1C3=CC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 JACPFCQFVIAGDN-UHFFFAOYSA-M 0.000 claims description 10
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
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- MOXZSKYLLSPATM-UHFFFAOYSA-N 1-(4-hydroxyphenyl)-2h-tetrazole-5-thione Chemical compound C1=CC(O)=CC=C1N1C(=S)N=NN1 MOXZSKYLLSPATM-UHFFFAOYSA-N 0.000 abstract description 6
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 6
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- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000006862 quantum yield reaction Methods 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
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- 238000011282 treatment Methods 0.000 description 4
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 229910004042 HAuCl4 Inorganic materials 0.000 description 3
- 206010034972 Photosensitivity reaction Diseases 0.000 description 3
- 229960005070 ascorbic acid Drugs 0.000 description 3
- 235000010323 ascorbic acid Nutrition 0.000 description 3
- 239000011668 ascorbic acid Substances 0.000 description 3
- 150000007980 azole derivatives Chemical class 0.000 description 3
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000000144 pharmacologic effect Effects 0.000 description 3
- 239000005049 silicon tetrachloride Substances 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- RZVCEPSDYHAHLX-UHFFFAOYSA-N 3-iminoisoindol-1-amine Chemical compound C1=CC=C2C(N)=NC(=N)C2=C1 RZVCEPSDYHAHLX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
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- SANFHSDFVUTGEA-UHFFFAOYSA-N dichlorosilicon(2+) Chemical compound Cl[Si+2]Cl SANFHSDFVUTGEA-UHFFFAOYSA-N 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- UUYKGYZJARXSGB-UHFFFAOYSA-N ethanol;ethoxy(trihydroxy)silane Chemical compound CCO.CCO[Si](O)(O)O UUYKGYZJARXSGB-UHFFFAOYSA-N 0.000 description 2
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- BBNQQADTFFCFGB-UHFFFAOYSA-N purpurin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC(O)=C3C(=O)C2=C1 BBNQQADTFFCFGB-UHFFFAOYSA-N 0.000 description 2
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- SIBAYCGJTMLDIQ-UHFFFAOYSA-N 21,23-dimethylporphyrin Chemical compound CN1C=2C=CC1=CC=1C=CC(=CC3=CC=C(N3C)C=C3C=CC(C=2)=N3)N=1 SIBAYCGJTMLDIQ-UHFFFAOYSA-N 0.000 description 1
- UJKPHYRXOLRVJJ-MLSVHJFASA-N CC(O)C1=C(C)/C2=C/C3=N/C(=C\C4=C(CCC(O)=O)C(C)=C(N4)/C=C4\N=C(\C=C\1/N\2)C(C)=C4C(C)O)/C(CCC(O)=O)=C3C Chemical class CC(O)C1=C(C)/C2=C/C3=N/C(=C\C4=C(CCC(O)=O)C(C)=C(N4)/C=C4\N=C(\C=C\1/N\2)C(C)=C4C(C)O)/C(CCC(O)=O)=C3C UJKPHYRXOLRVJJ-MLSVHJFASA-N 0.000 description 1
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- YICOVXASQKWWDU-UHFFFAOYSA-N ethanol;3-triethoxysilylpropan-1-amine Chemical compound CCO.CCO[Si](OCC)(OCC)CCCN YICOVXASQKWWDU-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
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- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
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- LKKPNUDVOYAOBB-UHFFFAOYSA-N naphthalocyanine Chemical compound N1C(N=C2C3=CC4=CC=CC=C4C=C3C(N=C3C4=CC5=CC=CC=C5C=C4C(=N4)N3)=N2)=C(C=C2C(C=CC=C2)=C2)C2=C1N=C1C2=CC3=CC=CC=C3C=C2C4=N1 LKKPNUDVOYAOBB-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229940109328 photofrin Drugs 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 239000013612 plasmid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 239000002904 solvent Substances 0.000 description 1
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- 125000001424 substituent group Chemical group 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
- A61K41/0052—Thermotherapy; Hyperthermia; Magnetic induction; Induction heating therapy
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
- A61K41/0057—Photodynamic therapy with a photosensitizer, i.e. agent able to produce reactive oxygen species upon exposure to light or radiation, e.g. UV or visible light; photocleavage of nucleic acids with an agent
- A61K41/0071—PDT with porphyrins having exactly 20 ring atoms, i.e. based on the non-expanded tetrapyrrolic ring system, e.g. bacteriochlorin, chlorin-e6, or phthalocyanines
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
- A61P31/04—Antibacterial agents
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- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Medicinal Chemistry (AREA)
- Veterinary Medicine (AREA)
- Organic Chemistry (AREA)
- Pharmacology & Pharmacy (AREA)
- Public Health (AREA)
- Epidemiology (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Communicable Diseases (AREA)
- Oncology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Biochemistry (AREA)
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- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention discloses a loaded bis- (1- (4-hydroxyphenyl) -5-mercapto-tetrazolyl) silicon phthalocyanine Russian nesting doll type nano gold rod system and a preparation method and application thereof. Firstly, synthesizing gold nanorods, then coating aminated silicon dioxide on the surfaces of the gold nanorods, and finally coating a layer of gold nanospheres on the surfaces of the gold nanorods with aminated silicon dioxide to prepare the Russian cottony doll type gold nanorods with a three-layer cavity structure. Reacting the dichlorosilicon phthalocyanine with 1- (4-hydroxyphenyl) -5-mercapto-tetrazole to synthesize the bis- (1- (4-hydroxyphenyl) -5-mercapto-tetrazole) silicon (IV) phthalocyanine. Finally, bis- (1- (4-hydroxyphenyl) -5-mercapto-tetrazolyl) silicon (IV) phthalocyanine and Russian nesting doll gold nanorods are prepared through a molecular assembly method to obtain the Russian nesting doll nano gold nanorod system loaded with bis- (1- (4-hydroxyphenyl) -5-mercapto-tetrazolyl) silicon phthalocyanine and the Russian nesting doll nano gold nanorod system used as photodynamic and photothermal therapy for combined inactivation of drug-resistant bacteria and tumors.
Description
Technical Field
The invention belongs to the field of nano biomedicine, and particularly belongs to a nano gold rod nano system loaded with azaphthalocyanine Russian dolls, a preparation method thereof and application thereof in photodynamic/photothermal therapy/photodynamic-photothermal synergistic inactivation of drug-resistant bacteria.
Background
Photodynamic Antibacterial Chemotherapy (PACT) is a promising new strategy for the treatment of refractory bacterial infectious diseases. The basic principle is as follows: the photosensitizer is preferentially and selectively enriched in bacteria, and is excited from a ground state to a triplet state under illumination; the triplet photosensitizer directly reacts with biological molecules to generate free radicals and/or free electrons (I type reaction), or reacts with molecular oxygen to generate higher-activity singlet oxygen (II type reaction); free radicals and singlet oxygen are toxic to target microorganisms, thereby inactivating bacteria and treating bacterial infectious diseases.
The factors that influence PACT mainly include bacterial cell wall structures and photosensitizers. To date, three generations of photosensitizers exist: the first generation of photosensitizers include hematoporphyrin derivative (HPD), dimethylporphyrin ether (DHE), and photosensitizer ii (photofrin ii), etc., and have the main disadvantages of weak absorption in the infrared region with strong penetration and high phototoxicity; the second-generation photosensitizer mainly comprises chlorophyll, phthalocyanine complex, purpurin, naphthalocyanine, iron pheophorbide, iron bacterial chlorophyllin and the like, wherein the phthalocyanine photosensitizer becomes the second-generation photosensitizer with potential application prospect due to the advantages that the phthalocyanine photosensitizer has the maximum absorption wavelength in a red light region, and has strong tissue penetration depth, low phototoxicity, high singlet oxygen quantum yield and the like; but the phthalocyanine molecule 18 electronic structure has high coplanarity and strong pi-pi hydrophobic effect, so that the phthalocyanine molecule is easy to gather in water, the fluorescence lifetime and the singlet oxygen quantum yield are reduced, and the photodynamic treatment effect is reduced. Therefore, the development of phthalocyanine photosensitizers with excellent performance is the focus of research.
The compound with the structure of five-membered aromatic heterocyclic ring containing nitrogen and sulfur heterocyclic ring is a medical synthetic intermediate with excellent performance. For example, the azole derivatives are mainly used as bactericides, and can be condensed with amino to form other novel compounds after carboxyl is introduced on the azole, so that the lipid solubility of the drugs is improved, and the bioavailability of the drugs is further increased. Therefore, if groups having pharmacological and biological activities (such as heterocyclic compounds containing nitrogen and sulfur) are introduced into the axial position of the phthalocyanine, not only can the solubility and dispersibility of the phthalocyanine be improved, but also the pharmacological properties and the crosslinking property with a drug-loading system can be exerted to improve the bioavailability.
The third-generation photosensitizer is adhered to or introduced into some 'chemical devices' with biological characteristics on the second-generation photosensitizer, the 'chemical devices' can transport or target the photosensitizer to specified tissues or cells, and biocompatibility and target tissue targeting are further improved, and the 'chemical devices' comprise liposomes, polymer micelles, single-walled carbon nanotubes, gold nanorods and the like.
The gold nanorods have a surface plasmon resonance effect, can enhance Raman and fluorescence effects of cross-linked molecules, and effectively convert light into heat, and are considered as an effective photothermal conductor. In addition, the gold nanorod has the characteristics of controllable size, easy modification, stable property, good biocompatibility and the like, and is used as an inorganic nano carrier with excellent performance. Further, mesoporous silica (SiO2) nanoparticles with controllable size, good biocompatibility, large surface area, pore channel and pore volume are coated on the surface of the gold nanorod to prepare AuNR @ SiO2, so that the toxicity of the gold nanorod can be remarkably reduced, the surface plasmon resonance of the gold nanorod is enhanced in a near-infrared region, the drug loading of the nanoparticles is improved, and the tumor treatment effect is enhanced [164 ]. To date, nanogold @ silica based is the only inorganic nano-drug carrier approved by the FDA for clinical trials in the treatment of cancer and cellular imaging.
Therefore, the novel Russian nesting doll type gold nanorod nano-particles with a three-layer structure are constructed, and then the Russian nesting doll type gold nanorod composite system loaded with the novel mercapto-nitrogen heterocyclic silicon (IV) phthalocyanine complex is prepared by assembling mercapto or adsorption of the mercapto-nitrogen heterocyclic silicon (IV) phthalocyanine and Russian nesting doll type gold nanorods.
Disclosure of Invention
The invention aims to provide a Russian nesting doll type nano gold rod nano system loaded with azaphthalocyanine, which is characterized in that: the Russian nesting doll type nano-gold rod system is of a three-layer cavity structure loaded with bis- (1- (4-hydroxyphenyl) -5-mercapto-tetrazolyl) axial substituted silicon phthalocyanine complex.
The invention also provides application of the supported azaphthalocyanine Russian nesting doll type nano gold rod nano system as a photosensitizer/photo-thermal agent.
The purpose of the invention is realized by that, the novel mercapto nitrogen heterocyclic ring silicon (IV) phthalocyanine complex is a compound with the following structure: the chemical formula is bis- (1- (4-hydroxyphenyl) -5-mercapto-tetrazolyl) silicon (IV) phthalocyanine (the patent refers to bis- (1- (4-hydroxyphenyl) -5-mercapto-tetrazolyl) silicon (IV) phthalocyanine for short is Tet-SiPc)
The novel sulfydryl nitrogen heterocyclic ring silicon (IV) phthalocyanine complex introduces nitrogen-containing sulfur heterocyclic ring groups with photo-physical-chemical, pharmacological and heterocyclic ring characteristics into the axial position of silicon (IV) phthalocyanine, and is expected to improve the dispersibility of the phthalocyanine and the cross-linking property of the phthalocyanine with a drug-carrying system.
The purpose of the invention is realized in such a way that the Russian nesting doll type nano gold rod with the three-layer cavity structure is a nano particle with the following structure: in the structure: the core is a gold nanorod, the middle layer is mesoporous silicon dioxide, and the outermost layer is a gold nanosphere.
The invention relates to a preparation method of bis- (1- (4-hydroxyphenyl) -5-mercapto-tetrazolyl) silicon (IV) phthalocyanine, which comprises the following steps:
1) in the presence of quinoline, 1, 3-diiminoisoindoline reacts with silicon tetrachloride (SiCl4) to synthesize dichlorosilicon (IV) phthalocyanine.
2) Reacting silicon dichloride (IV) phthalocyanine with 1- (4-hydroxyphenyl) -5-mercapto-tetrazole in a toluene solution in the presence of anhydrous potassium carbonate to synthesize di- (1- (4-hydroxyphenyl) -5-mercapto-tetrazole) axially substituted silicon (IV) phthalocyanine (di- (1- (4-hydroxyphenyl) -5-mercapto-tetrazole) for short Tet-SiPc)
The invention relates to a preparation method of a Russian nesting doll type nano gold rod with a three-layer cavity structure, which comprises the following specific steps:
1) under the condition of stirring, adding a new sodium borohydride solution into a Cetyl Trimethyl Ammonium Bromide (CTAB) solution and a chloroauric acid (HAuCl4) solution to obtain a gold nanorod (AuNR) seed solution, and standing for later use. And sequentially adding a Cetyl Trimethyl Ammonium Bromide (CTAB) solution, a chloroauric acid (HAuCl4) solution, a silver nitrate (AgNO3) solution, a hydrochloric acid (HCl) solution and an Ascorbic Acid (AA) solution into another conical flask, rapidly shaking, and finally adding a gold nanorod (AuNR) seed solution to prepare the gold nanorod (the gold nanorod is abbreviated as AuNR).
2) Under the condition of stirring, AuNR aqueous dispersion reacts with NaOH solution, 20% by volume ethyl orthosilicate ethanol solution and 2% by volume 3-aminopropyltriethoxysilane ethanol solution to synthesize an aminated silica-coated gold nanorod composite system (the silica-coated gold nanorod composite system is abbreviated as AuNR @ SiO2-NH 2).
3) Under the condition of stirring, gold nanorod water dispersion (sodium hydroxide solution, chloroauric acid solution and sulfhydryl polyethylene glycol solution are reacted, and fresh sodium borohydride (NaBH4) solution prepared by ice water is injected to prepare a Russian nesting doll type gold nanorod composite system (the Russian nesting doll type gold nanorod composite system is abbreviated as AuNR @ SiO2-NH2@ Au).
The preparation method of the Russian nesting doll gold nanorod composite system loaded with bis- (1- (4-hydroxyphenyl) -5-mercapto-tetrazolyl) silicon (IV) phthalocyanine comprises the steps of dispersing Russian nesting doll gold nanorods in secondary distilled water of 10M L, adding a DMSO solution of bis- (1- (4-hydroxyphenyl) -5-mercapto-tetrazolyl) axially substituted silicon (IV) phthalocyanine with the concentration of 50 mu L being 1 × 10-3M under the condition of stirring, reacting for 2 days at room temperature, washing and centrifuging for three times, and dispersing precipitates in secondary distilled water of 10M L to obtain the Russian nesting doll gold nanorod composite system loaded with bis- (1- (4-hydroxyphenyl) -5-mercapto-tetrazolyl) axially substituted silicon (IV) phthalocyanine.
The invention has the beneficial effects that: the invention takes silicon (IV) phthalocyanine complex as the center and nitrogen-sulfur heterocyclic group as axial substituent, on one hand, the azole derivative is mainly applied as bactericide, after carboxyl is introduced on the azole, the azole derivative can be condensed with amino to form other novel compounds, and simultaneously, the lipid solubility of the drug is improved, thereby increasing the bioavailability of the drug and enhancing the antibacterial effect. On the other hand, the nitrogenous-sulfur heterocyclic group has large steric hindrance, enhances the isolation protection effect on the core part, and has red shift of the absorption spectrum; silicon (IV) phthalocyanine nucleus does not form dimer under higher concentration, so the photosensitivity of the photosensitizer is improved, the fluorescence intensity is enhanced, the fluorescence quantum yield is generally higher, the singlet oxygen quantum yield still keeps higher level and the like.
The load bis- (1- (4-hydroxyphenyl) -5-mercapto-tetrazolyl) axially substituted silicon (IV) phthalocyanine Russian nesting doll gold nanorod composite system prepared by the invention has the following advantages: on one hand, the bis- (1- (4-hydroxyphenyl) -5-mercapto-tetrazolyl) axially substituted silicon (IV) phthalocyanine is dispersed in a silicon dioxide layer through Au-S bonds or adsorption, and the aggregation behavior of the phthalocyanine is inhibited to a certain extent, which is beneficial to increasing the yield of singlet oxygen quanta; on the other hand, the Russian nesting doll gold nanorod with the three-layer cavity structure has the following advantages: the plasma resonance absorption peak can be adjusted through the length-diameter ratio of the gold nanorods and the size of the mesoporous SiO2, and the position of the maximum absorption peak can be adjusted to the optimal window (near infrared region) of biological treatment; the three-layer cavity structure of the Russian nesting doll type nano gold rod can effectively absorb efficiency, convert light into heat and realize photothermal therapy; mesoporous SiO2 in the three-layer cavity structure can increase the loading capacity of the phthalocyanine complex photosensitizer. Therefore, the loaded bis- (1- (4-hydroxyphenyl) -5-mercapto-tetrazolyl) axially substituted silicon (IV) phthalocyanine Russian cotta type gold nanorod composite system is expected to realize the photodynamic-photothermal synergistic effect to eliminate drug-resistant bacteria, and can control the light-operated release of a photosensitizer and the generation of singlet oxygen to reduce the generation of drug resistance due to long-term contact.
Drawings
In order that the present invention may be more readily and clearly understood, a more particular description of the invention briefly described above will be rendered by reference to specific embodiments that are illustrated in the appended drawings.
Fig. 1 shows the light inactivation effect of russian nesting doll type nano gold rods with a three-layer cavity structure on escherichia coli, (a) the growth of treated bacteria on an L B plate, and (B) the viable bacteria statistics of the treated bacteria.
FIG. 2 shows the light-inactivating effect of a Russian nesting doll type gold nanorod and a loaded bis- (1- (4-hydroxyphenyl) -5-mercapto-tetrazolyl) axially substituted silicon phthalocyanine Russian nesting doll type gold nanorod composite system on Escherichia coli, (A) the growth of the treated bacteria on an L B plate, (B) the viable bacteria statistics of the treated bacteria, wherein Pc/Au represents the Russian nesting doll type gold nanorod and the loaded bis- (1- (4-hydroxyphenyl) -5-mercapto-tetrazolyl) axially substituted silicon phthalocyanine Russian nesting doll type gold nanorod composite system
Detailed Description
The present invention will be described in detail with reference to the following examples:
1) preparation of dichlorosilicon (IV) phthalocyanine
Adding 7.28g of 1, 3-diiminoisoindoline and 83m L of quinoline into a three-necked bottle, gradually heating to 60 ℃, adding 8.3m L of silicon tetrachloride, heating to 220 ℃, reacting for 30min, cooling to room temperature, pouring the reactant into 200m L methanol solution, ultrasonically stirring for 30min, standing for 1h, performing suction filtration, sequentially washing with solvents such as acetone, methanol, dichloromethane, acetone and the like, washing until the supernatant is clear, and drying to obtain 4.1256g of bluish-purple powdery solid (1), wherein the yield is 49.2%.
2) Preparation of bis- (1- (4-hydroxyphenyl) -5-mercapto-tetrazolyl) axially substituted silicon (IV) phthalocyanine
Adding 1- (4-hydroxyphenyl) -5-mercapto-tetrazole (0.0611 g), 1- (4-hydroxyphenyl) -5-mercapto-tetrazole (0.05826g), anhydrous potassium carbonate (0.0280g), toluene 30M L, heating to 110 ℃, refluxing for 48H, cooling to room temperature after the reaction is finished, filtering, concentrating the filtrate, purifying by using an aluminum oxide column chromatography with eluents (acetone/hexane (volume ratio is 1:5) and methanol/dichloromethane (volume ratio is 1:10)) for 2 times, performing column chromatography with acetone/dichloromethane (volume ratio is 1:10) as an eluent for 2 times, performing vacuum drying to obtain a dark blue-green solid substance 0.0164g, wherein the yield is 18%. IR (KBr/cm-1): 1610, 1506, 1429, 1240, 1080, 840, 736. Raman (cm-1): 1521524, 1342, ESI, 600.1H (400, 35 MHz:. DMSO-35, 1612, 17.8H-8 H.8, 18.8 H.8 Hz), M-926H 8 Hz (M-8H 8 H.8 Hz), M.8 Hz).
3) Preparation of gold nanorods
Cetyl trimethyl ammonium bromide (0.1M, 10M L) and chloroauric acid (50 μ L, 50mM) aqueous solution were added to an Erlenmeyer flask, and fresh sodium borohydride aqueous solution (600 μ L, 0.01M) was added under stirring, and after stirring for about 5min, the color of the solution changed from yellow to brown to obtain gold nanorod seed solution, which was left to stand at 25 ℃ for 2 h for backup.
In another erlenmeyer flask, cetyl trimethyl ammonium bromide (0.1M, 30M L) water solution, chloroauric acid (0.3M L, 50mM) water solution, silver nitrate (0.1M, 0.3M L) water solution, hydrochloric acid (1M, 0.3M L l) solution with concentration and ascorbic acid (0.1M, 0.24M L) water solution are added in sequence, the solution is shaken rapidly, the color of the solution is changed from orange yellow to colorless, finally, the gold nanorod seed solution prepared by the above steps is added, the obtained gold nanorods are stood for about 10 hours under the condition of 25 ℃, the prepared gold nanorods are washed with water and centrifuged for three times (10000rpm/10min), and the gold nanorods are diluted to 10M L by secondary distilled water.
4) Preparation of gold nanorods wrapped by aminated silicon dioxide
Washing the gold nanorod dispersion liquid prepared in the step three times by water and centrifuging (10000rpm/10min), transferring the gold nanorod dispersion liquid into an iodine measuring flask, adding 20M L secondary distilled water into the iodine measuring flask, adding NaOH (0.1M, 0.3M L) solution with concentration under the stirring condition, stirring for about 5 minutes, adding ethyl orthosilicate ethanol (20% by volume and 30 mu L) solution and 3-Aminopropyltriethoxysilane (APTES) ethanol solution (2% by volume and 10 mu L) at intervals of 30min, reacting for 24 hours in a water bath at 30 ℃, centrifugally washing the suspension three times (8500rpm/30min) after the reaction is finished, collecting precipitates, and re-dispersing the precipitates in 10M L secondary distilled water to prepare the gold nanorod composite system coated with the aminated silicon dioxide.
5) Preparation of Russian nesting doll type gold nanorod
Adding 5M L aqueous dispersion of the substance (7) prepared in the above step into a brown iodine measuring flask, diluting the aqueous dispersion to 9M L by using secondary distilled water, adding 10 mu L NaOH solution with concentration of 0.1M, 50 mu L chloroauric acid (HAuCl4) aqueous solution with concentration of 50mM and 50 mu L sulfhydryl polyethylene glycol (PEG-SH) aqueous solution with concentration of 1mM in sequence under stirring, reacting for 30min, quickly injecting newly prepared sodium borohydride (0.01M, 1M L) solution by ice water under stirring, reacting for 2 days at room temperature, after the reaction is finished, washing and centrifuging the mixture for three times (8500rpm/20min), and dispersing the precipitate in 10M L secondary distilled water to prepare the Russian cotta type gold nanorod.
6) Preparation of loaded di- (1- (4-hydroxyphenyl) -5-mercapto-tetrazolyl) axially substituted silicon phthalocyanine Russian nesting doll type gold nanorod composite system
Taking 10M L Russian cottony doll type gold nanorod water dispersion, adding a DMSO solution (1 × 10-3M, 50 mu L) of bis- (1- (4-hydroxyphenyl) -5-mercapto-tetrazolyl) axially substituted silicon (IV) phthalocyanine with concentration into the dispersion under stirring at room temperature for reaction for 2 days, washing and centrifuging the mixture for three times, and dispersing the precipitate into 10M L secondary distilled water to obtain the Russian cottony doll type gold nanorod system with the three-layer cavity structure of the supported bis- (1- (4-hydroxyphenyl) -5-mercapto-tetrazolyl) axially substituted silicon phthalocyanine complex.
7) Russian nesting doll type gold nanorod and loaded bis- (1- (4-hydroxyphenyl) -5-mercapto-tetrazolyl) axially substituted silicon phthalocyanine Russian nesting doll type gold nanorod composite system have light inactivation effect on common/resistant escherichia coli
Culturing bacteria, namely culturing E.coli DH5 α strain and E.coli DH5 α single strain in a shaking table overnight, placing a 96-hole plate, a 100m L pipette and a gun head in a super clean table for ultraviolet sterilization for 30min, taking out E.coli DH5 α suspension in the shaking table, fully oscillating the E.coli DH5 α in a culture solution of L B in a vortex oscillator for 2min to uniformly oscillating the E.coli DH5 α in the culture solution, taking 200m L suspension in the 96-hole plate by using the pipette in the super clean table, measuring an OD value at a wavelength of 600nm by using a multifunctional microplate reader, and diluting the OD value of the E.coli DH5 α bacteria solution to about 0.5, namely obtaining the logarithmic phase growth concentration of 5 × 107Bacteria suspension per m L.
Kanr、ZeorAnd AmprPreparation of resistant E.coli DH5 α preparation of samples containing Kan, scheme 25, preparation with calcium chloride and transformation of competent E.coli, Chapter I, molecular cloning instructions (third edition), scheme 25r、ZeorAnd AmprThe resistant plasmids pET-30, pPICZA and pUC18 are respectively transformed into E.coli DH5 α to obtain the corresponding resistant Escherichia coli.
Coli DH5 α light inactivation effect determination, in the experiment, the illumination condition of the illumination group is that firstly the wavelength is 808nm, and the power density is 500mW/cm2Irradiating with laser at 671nm and 100mW/cm2 for 10 min. Will OD600After the 0.5 bacterial suspension was treated as described above, each group of bacterial solutions was diluted 10-fold and 10-fold in sequence 210 times of310 times of410 times of510 times of6And (3) taking 2u L bacterial suspension by using a pipette gun, respectively inoculating the bacterial suspension to L B solid culture media, reversely putting the bacterial suspension into a constant-temperature incubator at 37 ℃, continuously culturing for 16h, comparing colony forming units of each group, and calculating the survival rate of the bacteria.
FIG. 2 shows the light inactivation effect of Tet-SiPc @ AuNR @ SiO2-NH2 on E.coli DH5 α, the solid culture medium live photographs inoculated with the bacterial liquid in step (A) before and after laser treatment and the statistics of the number of colonies in each group on the solid culture medium in step (B), and the results show that the loaded di- (1- (4-hydroxyphenyl) -5-mercapto-tetrazolyl) axially substituted silicon phthalocyanine Russian cotta gold nanorod composite system has obvious light inactivation effect on common/resistant E.coli DH5 α.
Claims (7)
1. The Russian nesting doll type nano gold rod nano system loaded with azaphthalocyanine in the claim 1 is characterized in that: the Russian nesting doll type nano-gold rod system is of a three-layer cavity structure and loads bis- (1- (4-hydroxyphenyl) -5-mercapto-tetrazolyl) axial substituted silicon phthalocyanine.
2. The Russian nesting doll type nano-gold rod of a three-layer cavity structure in claim 1, wherein: the nano-particle is the following nano-particle with a three-layer cavity structure: the inner core is a nano gold rod, the middle layer is mesoporous silicon dioxide, and the outer layer is a nano gold ball.
3. The mercaptoazacyclosilane (IV) phthalocyanine complex of claim 1, characterized in that: a compound of the following chemical structure: bis- (1- (4-hydroxyphenyl) -5-mercapto-tetrazolyl) axially substituted silicon phthalocyanines.
4. The bis- (1- (4-hydroxyphenyl) -5-mercapto-tetrazolyl) axially substituted silicon phthalocyanine of claim 1 is prepared by refluxing 1- (4-hydroxyphenyl) -5-mercapto-tetrazolyl with dichlorosilicon phthalocyanine in a toluene solution of anhydrous K2CO 3.
5. The preparation method of the Russian nesting doll type gold nanorod composite system loaded with the novel mercapto nitrogen heterocyclic silicon (IV) phthalocyanine complex, according to claim 1, is characterized in that: dispersing the Russian nesting doll type gold nano system in secondary distilled water, adding a DMSO solution of di- (1- (4-hydroxyphenyl) -5-mercapto-tetrazolyl) axially substituted silicon phthalocyanine into the Russian nesting doll type gold nano system under the condition of stirring, reacting at room temperature for 2 days, and then dispersing in the secondary distilled water again to prepare the gold nano system.
6. The novel Russian nesting doll type nano-gold rod with a three-layer cavity structure in claim 2 can be used for inactivating bacteria.
7. The Russian nesting doll type gold nanorod composite system loaded with the novel mercaptonitrogen heterocyclic silicon (IV) phthalocyanine complex is used as a photosensitizer/photothermal agent of a combined photodynamic and photothermal therapy for inactivating drug-resistant bacteria.
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| CN115819446A (en) * | 2022-11-02 | 2023-03-21 | 山东大学 | Phthalocyanine-fluorescein organic photo-thermal agent, preparation method thereof and application thereof in organic near-infrared photo-thermal treatment antitumor drugs |
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| CN114369960A (en) * | 2022-01-13 | 2022-04-19 | 武汉纺织大学 | Preparation method and application of photocuring antibacterial silicon dioxide coating |
| CN114369960B (en) * | 2022-01-13 | 2023-08-29 | 武汉纺织大学 | Preparation method and application of photo-cured antibacterial silicon dioxide coating |
| CN114538593A (en) * | 2022-02-21 | 2022-05-27 | 杭州师范大学钱江学院 | Application of hydrophobic phthalocyanine as heterogeneous catalyst in oxidizing phenol wastewater by hydrogen peroxide |
| CN114538593B (en) * | 2022-02-21 | 2022-10-21 | 杭州师范大学钱江学院 | Application of hydrophobic phthalocyanine as heterogeneous catalyst in oxidizing phenol wastewater by hydrogen peroxide |
| US11807559B2 (en) | 2022-02-21 | 2023-11-07 | Hangzhou Normal University | Application of hydrophobic phthalocyanine as heterogeneous catalyst in oxidizing phenol wastewater by hydrogen peroxide |
| US11912596B2 (en) | 2022-02-21 | 2024-02-27 | Hangzhou Normal University | Application of hydrophobic phthalocyanine as heterogeneous catalyst in oxidizing phenol wastewater by hydrogen peroxide |
| CN115819446A (en) * | 2022-11-02 | 2023-03-21 | 山东大学 | Phthalocyanine-fluorescein organic photo-thermal agent, preparation method thereof and application thereof in organic near-infrared photo-thermal treatment antitumor drugs |
| CN115819446B (en) * | 2022-11-02 | 2024-04-05 | 山东大学 | Phthalocyanine-fluorescein organic photothermal agent, preparation method thereof and application thereof in organic near infrared photothermal treatment of antitumor drugs |
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