CN113750235A - Inorganic nano MoSx/gamma-MnS composite material and preparation method and application thereof - Google Patents
Inorganic nano MoSx/gamma-MnS composite material and preparation method and application thereof Download PDFInfo
- Publication number
- CN113750235A CN113750235A CN202111273552.6A CN202111273552A CN113750235A CN 113750235 A CN113750235 A CN 113750235A CN 202111273552 A CN202111273552 A CN 202111273552A CN 113750235 A CN113750235 A CN 113750235A
- Authority
- CN
- China
- Prior art keywords
- mns
- gamma
- mos
- composite material
- inorganic nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910006275 γ-MnS Inorganic materials 0.000 title claims abstract description 114
- 229910003185 MoSx Inorganic materials 0.000 title claims abstract description 95
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 206010028980 Neoplasm Diseases 0.000 claims abstract description 31
- 229910001868 water Inorganic materials 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000000243 solution Substances 0.000 claims abstract description 25
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims abstract description 20
- 235000018417 cysteine Nutrition 0.000 claims abstract description 20
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 19
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 19
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 19
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 19
- 235000015393 sodium molybdate Nutrition 0.000 claims abstract description 19
- 239000011684 sodium molybdate Substances 0.000 claims abstract description 19
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 17
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims abstract description 16
- 238000011282 treatment Methods 0.000 claims abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 238000003745 diagnosis Methods 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000008273 gelatin Substances 0.000 claims description 25
- 108010010803 Gelatin Proteins 0.000 claims description 24
- 229920000159 gelatin Polymers 0.000 claims description 24
- 235000019322 gelatine Nutrition 0.000 claims description 24
- 235000011852 gelatine desserts Nutrition 0.000 claims description 24
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 239000002114 nanocomposite Substances 0.000 claims description 10
- 229920001184 polypeptide Polymers 0.000 claims description 9
- 108090000765 processed proteins & peptides Proteins 0.000 claims description 9
- 102000004196 processed proteins & peptides Human genes 0.000 claims description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 3
- 230000000259 anti-tumor effect Effects 0.000 abstract description 7
- 239000011734 sodium Substances 0.000 abstract description 3
- 238000009097 single-agent therapy Methods 0.000 abstract description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract 1
- 229910052708 sodium Inorganic materials 0.000 abstract 1
- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 description 27
- 210000004027 cell Anatomy 0.000 description 25
- 229920001021 polysulfide Polymers 0.000 description 21
- 239000005077 polysulfide Substances 0.000 description 19
- 150000008117 polysulfides Polymers 0.000 description 19
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 16
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 16
- 239000003642 reactive oxygen metabolite Substances 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 229960003180 glutathione Drugs 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 238000002560 therapeutic procedure Methods 0.000 description 11
- 210000003470 mitochondria Anatomy 0.000 description 9
- 201000011510 cancer Diseases 0.000 description 7
- -1 superoxide ion Chemical class 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 6
- 230000006907 apoptotic process Effects 0.000 description 6
- 239000003937 drug carrier Substances 0.000 description 6
- 238000011534 incubation Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 238000004088 simulation Methods 0.000 description 5
- 210000001519 tissue Anatomy 0.000 description 5
- UBJVUCKUDDKUJF-UHFFFAOYSA-N Diallyl sulfide Chemical compound C=CCSCC=C UBJVUCKUDDKUJF-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 108010024636 Glutathione Proteins 0.000 description 4
- 210000000805 cytoplasm Anatomy 0.000 description 4
- PFRGXCVKLLPLIP-UHFFFAOYSA-N diallyl disulfide Chemical compound C=CCSSCC=C PFRGXCVKLLPLIP-UHFFFAOYSA-N 0.000 description 4
- UBAXRAHSPKWNCX-UHFFFAOYSA-N diallyl trisulfide Chemical compound C=CCSSSCC=C UBAXRAHSPKWNCX-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000003384 imaging method Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000002595 magnetic resonance imaging Methods 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 206010006187 Breast cancer Diseases 0.000 description 3
- 208000026310 Breast neoplasm Diseases 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 102000006587 Glutathione peroxidase Human genes 0.000 description 3
- 108700016172 Glutathione peroxidases Proteins 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000034994 death Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 125000003802 stannylidene group Chemical group [H][Sn]([H])=* 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 230000035899 viability Effects 0.000 description 3
- 102000003952 Caspase 3 Human genes 0.000 description 2
- 108090000397 Caspase 3 Proteins 0.000 description 2
- 102000011727 Caspases Human genes 0.000 description 2
- 108010076667 Caspases Proteins 0.000 description 2
- 102100030497 Cytochrome c Human genes 0.000 description 2
- 108010075031 Cytochromes c Proteins 0.000 description 2
- 241000289669 Erinaceus europaeus Species 0.000 description 2
- 108010053070 Glutathione Disulfide Proteins 0.000 description 2
- 206010021143 Hypoxia Diseases 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910015667 MoO4 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000010523 cascade reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000013270 controlled release Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000003511 endothelial effect Effects 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- YPZRWBKMTBYPTK-BJDJZHNGSA-N glutathione disulfide Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@H](C(=O)NCC(O)=O)CSSC[C@@H](C(=O)NCC(O)=O)NC(=O)CC[C@H](N)C(O)=O YPZRWBKMTBYPTK-BJDJZHNGSA-N 0.000 description 2
- 230000007954 hypoxia Effects 0.000 description 2
- 230000002147 killing effect Effects 0.000 description 2
- 230000003859 lipid peroxidation Effects 0.000 description 2
- 230000001404 mediated effect Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000002428 photodynamic therapy Methods 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000009214 sonodynamic therapy Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000004083 survival effect Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 230000001225 therapeutic effect Effects 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- 238000000584 ultraviolet--visible--near infrared spectrum Methods 0.000 description 2
- 210000003606 umbilical vein Anatomy 0.000 description 2
- 230000002792 vascular Effects 0.000 description 2
- JDLKFOPOAOFWQN-VIFPVBQESA-N Allicin Natural products C=CCS[S@](=O)CC=C JDLKFOPOAOFWQN-VIFPVBQESA-N 0.000 description 1
- 241000124008 Mammalia Species 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- JDLKFOPOAOFWQN-UHFFFAOYSA-N allicin Chemical compound C=CCSS(=O)CC=C JDLKFOPOAOFWQN-UHFFFAOYSA-N 0.000 description 1
- 235000010081 allicin Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000006851 antioxidant defense Effects 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000003833 cell viability Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002512 chemotherapy Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 238000009169 immunotherapy Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000004968 inflammatory condition Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000037353 metabolic pathway Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011275 oncology therapy Methods 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 150000008116 organic polysulfides Chemical class 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 230000004792 oxidative damage Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035778 pathophysiological process Effects 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 238000007626 photothermal therapy Methods 0.000 description 1
- 230000004962 physiological condition Effects 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000001959 radiotherapy Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000019086 sulfide ion homeostasis Effects 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000011277 treatment modality Methods 0.000 description 1
- 210000004881 tumor cell Anatomy 0.000 description 1
Images
Classifications
-
- 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
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/06—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
- A61K47/16—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite containing nitrogen, e.g. nitro-, nitroso-, azo-compounds, nitriles, cyanates
- A61K47/18—Amines; Amides; Ureas; Quaternary ammonium compounds; Amino acids; Oligopeptides having up to five amino acids
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/42—Proteins; Polypeptides; Degradation products thereof; Derivatives thereof, e.g. albumin, gelatin or zein
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/06—Nuclear magnetic resonance [NMR] contrast preparations; Magnetic resonance imaging [MRI] contrast preparations
- A61K49/08—Nuclear magnetic resonance [NMR] contrast preparations; Magnetic resonance imaging [MRI] contrast preparations characterised by the carrier
- A61K49/10—Organic compounds
- A61K49/14—Peptides, e.g. proteins
-
- 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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P35/00—Antineoplastic agents
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- General Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Epidemiology (AREA)
- Medicinal Chemistry (AREA)
- Pharmacology & Pharmacy (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Radiology & Medical Imaging (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Acoustics & Sound (AREA)
- Organic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
- Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)
Abstract
The invention discloses an inorganic nano MoSxA/gamma-MnS composite material, a preparation method and an application thereof belong to the technical field of anti-tumor and overcome the limitation of monotherapy in the prior art. Inorganic nano MoSxThe preparation method of the/gamma-MnS composite material comprises the following steps: step S1, respectively adding sodium molybdate, manganese sulfate and cysteine into water to be dissolved to obtain a sodium molybdate solution, a manganese sulfate solution and a cysteine solution; step S2, mixing molybdic acidMixing and stirring a sodium solution, a manganese sulfate solution and a cysteine solution to obtain a mixed solution; step S3, putting the mixed solution into a reaction kettle for hydrothermal reaction, cooling to room temperature after the hydrothermal reaction is finished, centrifuging and washing to obtain inorganic nano MoSxa/gamma-MnS heterojunction composite material. Inorganic nano MoS of the inventionxthe/gamma-MnS composite material can be applied to tumor diagnosis and treatment.
Description
Technical Field
The invention relates to the technical field of anti-tumor, in particular to inorganic nano MoSx[ gamma ] -MnS composite material anda preparation method and application thereof.
Background
Cancer is one of killers threatening human health, and improving the therapeutic effect of cancer becomes a hotspot and difficulty in the biomedical research field. The main clinical cancer therapies are surgery, chemotherapy and radiotherapy. In recent years, new therapeutic approaches including photodynamic therapy (PDT), sonodynamic therapy (SDT), photodynamic therapy (RDT), photothermal therapy, immunotherapy, etc. have been rapidly developed, and nanocatalysis therapy has recently been used for tumor therapy. Nanocatalysis therapy is an emerging tumor-specific treatment modality that induces apoptosis of tumor cells by selectively triggering catalytic chemical reactions within the Tumor Microenvironment (TME), primarily based on the use of non-toxic/low-toxic nanomaterials and the production of toxic products therefrom, such as Reactive Oxygen Species (ROS), which, due to the absence of such chemical reactions in normal tissues/organs, renders nanocatalysis therapy without significant side effects.
However, all of the above novel therapies, including nanocatalysis, use only one reactant, O2、H2O2Or H2O production of reactive oxygen species ROS (superoxide ion O)2·-Singlet oxygen1O2Or hydroxyl radical. OH), the effect of the nano-catalysis therapy in cancer diagnosis and treatment has certain limitation at present.
Disclosure of Invention
In view of the above analysis, the present invention aims to provide an inorganic nano-MoSxThe invention relates to a/gamma-MnS composite material, a preparation method and application thereof, and inorganic nano MoSxthe/gamma-MnS composite material has a better anti-tumor function and can overcome the limitation of the existing monotherapy.
The purpose of the invention is mainly realized by the following technical scheme:
in one aspect, the present invention provides an inorganic nano-MoSxThe preparation method of the/gamma-MnS composite material comprises the following steps:
step S1, respectively adding sodium molybdate, manganese sulfate and cysteine into water to be dissolved to obtain a sodium molybdate solution, a manganese sulfate solution and a cysteine solution;
step S2, mixing and stirring the sodium molybdate solution, the manganese sulfate solution and the cysteine solution to obtain a mixed solution;
step S3, putting the mixed solution into a reaction kettle for hydrothermal reaction, cooling to room temperature after the hydrothermal reaction is finished, centrifuging and washing to obtain inorganic nano MoSxa/gamma-MnS heterojunction composite material.
Further, in the step S1, the molar ratio of the sodium molybdate to the manganese sulfate to the cysteine is 2-3: 1-2: 8-13.
Further, in the step S1, the mass-to-volume ratio of the sodium molybdate to the water is 0.1-0.2 g: 3-6 mL.
Further, in the step S1, the mass-to-volume ratio of manganese sulfate to water is 0.025-0.05 g: 3-6 mL.
Further, in the step S1, the mass-to-volume ratio of the cysteine to the water is 0.2-0.5 g: 3-8 mL.
Further, in the step S3, the temperature of the hydrothermal reaction is 160-200 ℃, and the reaction time is 20-30 hours.
Further, the preparation method further comprises the following steps:
step S4, inorganic nano MoSxAdding the/gamma-MnS heterojunction composite material into water, adding gelatin, performing ultrasonic treatment until the gelatin is completely dissolved, stirring at room temperature, centrifuging, and washing to obtain MoSxthe/gamma-MnS @ Gel nano composite material.
Further, the preparation method further comprises the following steps:
s4, mixing inorganic nano MoSxAdding the/gamma-MnS heterojunction composite material into water, then adding gelatin and polypeptide cRGD, performing ultrasonic treatment until the gelatin and the polypeptide cRGD are completely dissolved, stirring at room temperature, then centrifuging, and washing to obtain MoSxthe/gamma-MnS @ Gel-cRGD nano composite material.
On the other hand, the invention also provides inorganic nano MoSxa/gamma-MnS composite material, the inorganic nano MoSxthe/gamma-MnS composite material is prepared by the preparation method.
The invention also provides a medicineMechanical nano MoSxThe application of the/gamma-MnS composite material is to use the composite material in tumor diagnosis and treatment.
Compared with the prior art, the invention can realize at least one of the following beneficial effects:
(1) MoS of the inventionxComprehensive utilization of inorganic nano MoS by using/gamma-MnS heterojunction composite materialxAnd the advantages of gamma-MnS, the nano MoSxAnd gamma-MnS, polysulfide and H2The controlled release source of S can ensure that MoSxGood NIR-II (1064nm) photothermal conversion performance of/gamma-MnS, and promotion of Mn release from metastable gamma-MnS while improving tumor hypoxia through photothermal under acidic TME (such as pH 6.5) response2+And H2S, performing ROS-mediated catalytic CDT, and MoSxDegradation and gamma-MnS released H2S can generate H polysulfide under the action of TME and NIR2Sn. Released H2S and polysulfide H2SnThe compound can act on cell mitochondria, so that the membrane potential of the mitochondria is reduced, the membrane permeability of the mitochondria is increased, the apoptosis promoting factor-cytochrome c in the mitochondria is released into cytoplasm, after the cytochrome c is released into the cytoplasm, the effect Caspase 3 is further activated, the Caspase cascade reaction is started, and finally the cell apoptosis is caused. In addition, MoSxthe/gamma-MnS also catalyzes the over-expressed reduced glutathione GSH in the TME to be oxidized GSSG, so that the ROS in the tumor can be efficiently accumulated, and the reduced glutathione GSH indirectly acts on glutathione peroxidase (GPX 4) in cells to reduce the oxidation resistance of the cells, so that the cells generate lipid peroxidation to cause oxidative death of the cells, and finally the CDT synergistic polysulfide/H promoted by NIR-II light heat is realized2S has the function of synergy and anti-tumor.
(2) MoS of the inventionxthe/gamma-MnS @ Gel has the performance of high Near Infrared (NIR) photothermal conversion efficiency and good water solubility and biocompatibility in a biological simulation system, so that the Gel can be used as a nano-drug carrier and can also be applied to tumor diagnosis and treatment.
(3)MoSxthe/gamma-MnS @ Gel-cRGD has good water solubility and biocompatibility in a biological simulation system, so that the carrier can be used as a nano-drug carrier; MoSxthe/gamma-MnS @ Gel-cRGD can be delivered to specific tumor tissues in a targeted mode, and efficient targeted tumor diagnosis and treatment of Magnetic Resonance Imaging (MRI)/photoacoustic imaging (PAT) navigation is achieved.
(4) The preparation method is simple and easy to implement, does not need a complex operation process, and is green, environment-friendly, high in yield and wide in application range.
In the invention, the above technical schemes can be combined with each other to realize more preferable combination schemes. Additional features and advantages of the invention will be set forth in the description which follows, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and drawings.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention, wherein like reference numerals are used to indicate like parts throughout.
In FIG. 1, a is the MoS of example 1 of the present inventionxScanning electron microscope picture of/gamma-MnS, b is MoS of example 1 of the present inventionx(transmission electron microscopy) of/gamma-MnS, c is MoS of example 1 of the inventionx(gamma-MnS @ Gel) as shown in the transmission electron microscope, and d is the MoS of example 1 of the present inventionxA high resolution transmission electron microscopy image of/gamma-MnS @ Gel;
FIG. 2 shows MoSxgamma-MnS and MoS of the inventionxAn X-ray diffraction spectrum of/gamma-MnS @ Gel;
FIG. 3 shows MoSx[ gamma ] -MnS (abbreviated MMS), MoSx[ gamma ] -MnS @ Gel (abbreviated as MMSG) and MoSxZeta potential of/gamma-MnS @ Gel-cRGD (abbreviated as MMSGR).
In FIG. 4, a is MoSxgamma-MnS and MoSxUV-Vis-NIR absorption spectrum of/gamma-MnS @ Gel; b is MoS of different concentrationsxLaser (0.8W cm) of/gamma-MnS @ Gel composite material at 1064nm-210min) temperature rise curve; c is a linear relation between time obtained in a cooling period when the 1064nm laser is turned off and-ln theta;
in FIG. 5, a is TA detection of MoSxCatalyst H of/gamma-MnS @ Gel2O2The Fenton reaction of (2) generates hydroxyl free radicals and the influence of Laser on the generation of the hydroxyl free radicals; b is MoSx[ gamma ] -MnS @ Gel in different media (pH variation and H thereof)2O2Presence or absence of) the hydrogen sulfide produced; c is pH vs MoSxThe effect of/γ -MnS @ Gel on polysulfide production and the consumption of polysulfide by GSH; d is MoSxConsumption of GSH by/γ -MnS @ Gel over time;
in FIG. 6, a is 4T1 breast cancer cells and HUVEC human umbilical vein vascular endothelial normal cells with different concentrations of MoSxCell viability after incubation for 12 h/gamma-MnS @ Gel-cRGD; b is MoS with different concentrations under different treatment conditionsxCell viability after incubation of/γ -MnS @ Gel-cRGD with 4T1 for 12 h.
Detailed Description
The preferred embodiments of the present invention will now be described in detail with reference to the accompanying drawings, which form a part hereof, and which together with the embodiments of the invention serve to explain the principles of the invention and not to limit its scope.
Currently, chemical kinetic Therapy (CDT) based on Fenton (Fenton) reaction has attracted more and more attention as an emerging typical nanocatalysis Therapy, generating Fe2+、Ti3+、Mn2+、Co2+And Cu+The nanomaterial of (a) is a typical Fenton or Fenton-like reagent, which mainly utilizes endogenous chemical substances (such as H) excessively generated under inflammatory conditions in the slightly acidic TME of the tumor2O2) ROS such as highly toxic OH are produced to kill cancer cells. The research finds that: cancer cells may evolve multiple reaction pathways in order to combat toxic ROS, either exogenously or produced by the cancer cells' own metabolism. For example, Glutathione (GSH) has antioxidant defense effects that protect cells from free radical oxidative damage, and is expressed in TME in much higher amounts than normal cells (4-fold higher than in normal cells); if GSH is not exhausted in time, the efficacy of ROS-based tumor therapy will be greatly affected; thus, it is exposed to H in endogenous TME2O2Insufficient reaction kinetics and levels to sustain sustained ROS induction and antioxidant defenseThe influence of the mechanism, the antitumor effect of the single novel therapy has certain limitation. H is adjusted by designing a high-performance Fenton catalyst and simultaneously applying different internal and external strategies2O2The reaction parameters such as concentration, tumor part reaction temperature and the like can improve the dynamics of the Fenton reaction, enhance the Fenton reaction to the maximum extent and be better used for treating tumors, but the reaction parameters are not well realized at present.
In recent years, gas therapy, which is a treatment using a specific gas to suppress tumors, has become a novel effective treatment with few side effects. To date, three major gas molecules have been studied, including carbon monoxide (CO), carbon monoxide (NO), and hydrogen sulfide (H)2S)。H2S is an endogenous gas signal molecule present in the body of a mammal and plays an important role in various physiological and pathophysiological processes. Notably, H2S naturally has fewer side effects on healthy cells due to its endogenous nature associated with multiple metabolic pathways. It is reported that H2The precursors of S are mainly organic polysulfides, such as allicin, which is unstable under physiological conditions and rapidly converts to alkyl sulfides, such as diallyl disulfide (DADS), diallyl trisulfide (DATS) and diallyl sulfide (DAS); these transformation products are active ingredients that inhibit bacterial growth; however, many organosulfur compounds are volatile, produce an unpleasant odor and are poorly water soluble, further limiting their widespread biological and clinical medical use. Studies have also found that polysulfides can efficiently produce H via a thiol-polysulfide cleavage mechanism2And S. Notably, TME is richer in thiols than healthy tissue, which naturally confers polysulfide tumor-specific H2And S is released.
The invention provides inorganic nano MoSxThe preparation method of the/gamma-MnS composite material comprises the following steps:
step S1, adding sodium molybdate (Na)2MoO4) Manganese sulfate (MnSO)4) And cysteine (L-Cys) are respectively added into water to be dissolved to obtain sodium molybdate solution and sulfurManganese acid solution and cysteine solution;
step S2, mixing and stirring the sodium molybdate solution, the manganese sulfate solution and the cysteine solution to obtain a mixed solution;
step S3, putting the mixed solution into a polytetrafluoroethylene reaction kettle for hydrothermal reaction, cooling to room temperature after the hydrothermal reaction is finished, centrifuging and washing to obtain inorganic nano MoSx[ gamma ] -MnS heterojunction composite Material (hereinafter abbreviated as MoS)x/γ-MnS)。
Specifically, in the step S1, the molar ratio of the sodium molybdate, the manganese sulfate and the cysteine is 2-3: 1-2: 8-13. Preferably, the molar ratio of the elements Mo and Mn is controlled to be 2: 1.
Specifically, in step S1, in order to reduce the influence of impurities, the water used may be deionized water.
Specifically, in the step S1, the mass-to-volume ratio of the sodium molybdate to the water is 0.1-0.2 g: 3-6 mL.
Specifically, in the step S1, the mass-to-volume ratio of manganese sulfate to water is 0.025-0.05 g: 3-6 mL.
Specifically, in the step S1, the mass-to-volume ratio of cysteine to water is 0.2-0.5 g: 3-8 mL.
Specifically, in step S1, in order to accelerate the dissolution of sodium molybdate, manganese sulfate and cysteine, ultrasonic dissolution may be used.
Specifically, in the step S2, the stirring may be performed by magnetic stirring at room temperature for 20-40 min, such as 20min, 25min, 30min, 35min, and 40 min.
Specifically, in step S3, in order to ensure sufficient hydrothermal reaction, the temperature of the hydrothermal reaction is controlled to be 160 to 200 ℃, for example, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃; the reaction time is 20-30 h, such as 20h, 22h, 24h, 26h, 28h and 30 h.
Specifically, in the step S3, the centrifugation process may be performed at 12000-12500 rpm for 3-8 min.
Specifically, in step S3, in order to clean and reduce impurity contamination, the washing may be performed by alternately washing with deionized water and ethanol for multiple times.
Specifically, the MoS obtained in step S3 isxthe/gamma-MnS is black hollow hedgehog-shaped particles, and the diameter of the particles is about 180-240 nm.
Specifically, the MoS obtained in step S3 isxthe/gamma-MnS has the performance of high Near Infrared (NIR) photothermal conversion efficiency.
Specifically, the MoS obtained in step S3 isxIn the/gamma-MnS, the range of x is 1-8.
Specifically, the MoS obtained in step S3 isxthe/gamma-MnS can be applied to tumor diagnosis and treatment.
In addition, the inorganic nano MoSxThe sulfide is a typical two-dimensional layered transition metal sulfide, and has the advantages of large specific surface area, high Near Infrared (NIR) photothermal conversion efficiency, high intake in TME, easy surface modification, easy biodegradation and the like; and the metastable state structure of gamma-MnS is easy to decompose under slightly acidic condition to generate Mn2+And H2S，Mn2+In the Fenton-like reaction in acidic TME, over-expressed H can be obtained2O2Is converted into OH. MoS obtained by the inventionxComprehensive utilization of inorganic nano MoS by using/gamma-MnS heterojunction composite materialxAnd the advantages of gamma-MnS, the nano MoSxAnd gamma-MnS, polysulfide and H2The controlled release source of S can ensure that MoSxGood NIR-II (1064nm) photothermal conversion performance of/gamma-MnS, and promotion of Mn release from metastable gamma-MnS while improving tumor hypoxia through photothermal under acidic TME (such as pH 6.5) response2+And H2S, performing ROS-mediated catalytic CDT, and MoSxDegradation to give polysulphides H2Sn. Released H2S and polysulfide H2SnThe compound can act on cell mitochondria, so that the membrane potential of the mitochondria is reduced, the membrane permeability of the mitochondria is increased, the apoptosis promoting factor-cytochrome c in the mitochondria is released into cytoplasm, after the cytochrome c is released into the cytoplasm, the effect Caspase 3 is further activated, the Caspase cascade reaction is started, and finally the cell apoptosis is caused. In addition, MoSxthe/gamma-MnS also catalyzes the over-expressed reduced glutathione GSH in TME to be oxidized GSSG, on the one handThe ROS in the tumor can be efficiently accumulated, on the other hand, the ROS indirectly acts on glutathione peroxidase (GPX 4) in cells, so that the oxidation resistance of the cells is reduced, the cells generate lipid peroxidation, the oxidative death of the cells is caused, and the NIR-II photo-thermal triggering CDT (glutathione peroxidase)/H (hydrogen sulfide) synergistic polysulfide is finally realized2S has the function of synergy and anti-tumor.
To improve MoSxThe biocompatibility of/gamma-MnS, the MoS can be modified by gelatin (abbreviated as Gel)x/γ-MnS。
Specifically, the preparation method further comprises:
step S4, MoSxadding/gamma-MnS into water, adding gelatin, performing ultrasonic treatment until the gelatin is completely dissolved, stirring at room temperature, centrifuging, and washing to obtain MoSx[ gamma ] -MnS @ Gel nanocomposite (hereinafter abbreviated as MoS)x,/γ -MnS @ Gel or MMSG).
Specifically, in step S4, in order to reduce the influence of impurities, the water used may be deionized water.
Specifically, in step S4, MoSxThe mass-volume ratio of the/gamma-MnS to the water is 0.01-0.02 g: 10-20 mL.
Specifically, in step S4, MoSxThe mass ratio of the/gamma-MnS to the gelatin is 1-1.5: 1-2.
Specifically, in the step S4, the stirring speed at room temperature is 1000 to 1200rpm, and the stirring time is 5 to 7 hours.
Specifically, in the step S4, the rotation speed is 12000-12500 rpm and the centrifugation time is 3-8 min during the centrifugation process.
Specifically, in the step S4, the washing process uses deionized water to wash off the excessive gelatin, so as to obtain MoSxthe/gamma-MnS @ Gel nano composite material.
Specifically, MoSxThe structure of the/gamma-MnS @ Gel is hollow hedgehog shaped nano particles.
Note that MoSxthe/gamma-MnS @ Gel has high near infrared light thermal conversion efficiency and good water solubility and biocompatibility in a biological simulation system, thereby being used as a nano-drug carrier and being capable of being used as a nano-drug carrierCan be applied to tumor diagnosis and treatment.
In one possible design, to improve MoSxThe biocompatibility and applicability of the/gamma-MnS to specific tumor tissues can further modify MoS by using gelatin and polypeptide cRGDx/γ-MnS。
Specifically, the preparation method further comprises:
s4, MoSxadding/gamma-MnS into water, then adding gelatin and polypeptide cRGD, performing ultrasonic treatment until the gelatin and the polypeptide cRGD are completely dissolved, stirring at room temperature, then centrifuging and washing to obtain MoSxthe/gamma-MnS @ Gel-cRGD nano composite material.
Specifically, in S4, the water used for reducing the influence of impurities may be deionized water.
Specifically, in S4, MoSxThe mass-volume ratio of the/gamma-MnS to the water is 0.01-0.02 g: 10-20 mL.
Specifically, in S4, MoSxThe mass ratio of the/gamma-MnS to the gelatin to the polypeptide cRGD is 1-1.5: 1-2: 0.5-1.
Specifically, in the step S4, the stirring speed at room temperature is 1000 to 1200rpm, and the stirring time is 5 to 7 hours.
Specifically, in the step S4, the rotation speed is 12000-12500 rpm and the centrifugation time is 3-8 min during the centrifugation process.
Specifically, in the step S4, the extra gelatin is washed away by deionized water in the washing process to obtain MoSxthe/gamma-MnS @ Gel-cRGD nano composite material.
Specifically, in S4, MoSxThe particle diameter of the/gamma-MnS @ Gel-cRGD is about 200-240 nm.
Note that MoSxthe/gamma-MnS @ Gel-cRGD has the performance of high Near Infrared (NIR) photothermal conversion efficiency and good water solubility and biocompatibility in a biological simulation system, so that the nano-drug carrier can be used as a nano-drug carrier and can be applied to tumor diagnosis and treatment.
MoS obtained by the inventionxthe/gamma-MnS @ Gel-cRGD has good water solubility and biocompatibility in a biological simulation system, so that the carrier can be used as a nano-drug carrier; MoSxthe/gamma-MnS @ Gel-cRGD canThe target delivery is carried out to specific tumor tissues, and the efficient target tumor diagnosis and treatment of Magnetic Resonance Imaging (MRI)/photoacoustic imaging (PAT) navigation is realized. MoS of the inventionxOn one hand, the photothermal effect of/gamma-MnS @ Gel-cRGD under the action of NIR-II (1064nm) promotes the decomposition of gamma-MnS and the Fenton-like reaction, the active oxygen (ROS) is increased, and the generated polysulfide H2Sn、H2S consumes GSH, which in turn leads to cell iron death; on the other hand to polysulphides H2Sn、H2Simultaneous production of S, acting on mitochondria to induce apoptosis, Mn2+The release of (A) also enhances MRI, NIR-II photothermal for PAT imaging, and finally NIR photothermal driven polysulfides and H for MRI/PAT imaging navigation2S synergizes with CDT to achieve the goal of antitumor effect.
The preparation method is simple and easy to implement, does not need a complex operation process, and is simple, green, environment-friendly, high in yield and wide in application range.
Example 1
This example provides an inorganic nano-MoSxThe preparation method of the/gamma-MnS composite material comprises the following steps:
(1) 0.1g (0.4856mmol) of sodium molybdate (Na)2MoO4) 0.0367g (0.2428mmol) manganese sulfate (MnSO)4) And 0.32g (2.6411mmol) of cysteine (L-Cys) (molar ratio of elements Mo: Mn ═ 2:1) were added to 3mL, and 4mL of deionized water, respectively, and the three solutions were mixed after ultrasonic dissolution.
(2) Placing the mixed solution at room temperature, magnetically stirring for 30min, placing the mixed solution into a polytetrafluoroethylene reaction kettle with a volume of 50mL, reacting for 24h at 180 ℃, cooling to room temperature, centrifuging at 12000rpm for 5min, and alternately washing with deionized water and ethanol for three times to obtain black MoSxa/gamma-MnS heterojunction composite material.
(3) Get MoSxAdding 0.01g of/gamma-MnS heterojunction composite material into 10mL of deionized water, adding 0.01g of gelatin, performing ultrasonic treatment until the gelatin is completely dissolved, stirring at the rotating speed of 1000rpm for 6h at room temperature, centrifuging at the rotating speed of 12000rpm for 5min, and washing off excessive gelatin by using deionized water to obtain MoSxthe/gamma-MnS @ Gel nano composite material.
Example 2
This example provides an inorganic nano-MoSxThe first two steps of the preparation method of the/gamma-MnS composite material are the same as (1) to (2) in the above example 1, and the preparation method comprises the following steps which are not repeated here:
(3) get MoSxAdding 0.01g of/gamma-MnS heterojunction composite material into 10mL of deionized water, adding 0.01g of gelatin and 0.005g of polypeptide cRGD, ultrasonically treating until the materials are completely dissolved, stirring at the rotating speed of 1000rpm for 6h at room temperature, centrifuging at the rotating speed of 12000rpm for 5min, and washing off excessive gelatin by using deionized water to obtain MoSxthe/gamma-MnS @ Gel-cRGD nano composite material.
Specifically, MoSx、γ-MnS、MoSx/γ-MnS、MoSx[ gamma ] -MnS @ Gel and MoSxThe results of various related detections of/gamma-MnS @ Gel-cRGD are as follows:
test example 1
Scanning electron microscope and transmission electron microscope observations.
As shown in FIG. 1, a is the MoS of example 1 of the present inventionxScanning electron microscope picture of/gamma-MnS, b is MoS of example 1 of the present inventionx(transmission electron microscopy) of/gamma-MnS, c is MoS of example 1 of the inventionx(gamma-MnS @ Gel) as shown in the transmission electron microscope, and d is the MoS of example 1 of the present inventionxHigh resolution transmission electron microscopy images of/γ -MnS @ Gel.
Wherein, as can be seen from the diagrams a, b and c, the MoS obtained in the embodimentx[ gamma ] -MnS and MoSxThe structure of the/gamma-MnS @ Gel is hollow hedgehog shaped nano-particles, MoSxThe diameter of the/gamma-MnS is about 180-240 nm; MoS obtained in cxThe particle diameter of/gamma-MnS @ Gel is about 240 nm; MoS can be seen from the high resolution transmission electron microscopy image in dxA heterojunction is formed with the gamma-MnS.
Test example 2
FIG. 2 shows MoSxgamma-MnS and MoS of the inventionxX-ray diffraction spectrum of/gamma-MnS @ Gel. As evidenced by the spectra, and MoS synthesized separatelyxCompared with gamma-MnS, the invention successfully adopts a hydrothermal methodObtain MoSxThe composite material is/gamma-MnS @ Gel.
Test example 3
MoSx[ gamma ] -MnS (abbreviated MMS), MoSx[ gamma ] -MnS @ Gel (abbreviated as MMSG) and MoSxZeta potential of/gamma-MnS @ Gel-cRGD (abbreviated as MMSGR).
As can be seen from FIG. 3, MoSxthe/gamma-MnS is positively charged, and the zeta potential of the positive charge is +5.30 mV; MoS obtained after modification of gelatinxThe potential of the/gamma-MnS @ Gel is changed to be negative (-13mV), which indicates that the gelatin is successfully modified to MoSxOn the/gamma-MnS, the stability of the material is enhanced; after the final modification of cRGD, the potential becomes positive (+7mV), which indicates that the cRGD is successfully modified to MoSxon/gamma-MnS @ Gel.
Test example 4
In FIG. 4, a is MoSxgamma-MnS and MoSxUV-Vis-NIR absorption spectrum of/gamma-MnS @ Gel; b is MoS of different concentrationsxLaser (0.8W cm) of/gamma-MnS @ Gel composite material at 1064nm-210min) temperature rise curve; c is a linear relationship of the time obtained during the cooling period when the 1064nm laser is turned off to-ln theta.
As can be seen from FIG. a, MoSxthe/gamma-MnS @ Gel composite material has the light-heat conversion performance when having the absorption in NIR-II (900nm-1400 nm); b it can be seen that with MoSxThe concentration of the/gamma-MnS @ Gel composite material is increased, and the temperature is gradually increased; MoS can be obtained in cxThe photothermal conversion efficiency of the/gamma-MnS @ Gel is 45.07%.
Test example 5
In FIG. 5, a is TA detection of MoSxCatalyst H of/gamma-MnS @ Gel2O2The Fenton reaction of (2) generates hydroxyl free radicals and the influence of Laser on the generation of the hydroxyl free radicals; b is MoSx[ gamma ] -MnS @ Gel (hereinafter abbreviated as MMSG) in different media (change of pH value and H thereof)2O2Presence or absence of) the hydrogen sulfide produced; c is the effect of pH on the production of polysulfides by MMSG and the consumption of polysulfides by GSH; d is the consumption of GSH by the MMSG over time.
As can be seen from a in fig. 5, the temperature has an accelerating effect on the generation of hydroxyl radicals by the Fenton reaction. B shows that the lower the pH value of the generated hydrogen sulfide, the more the generated hydrogen sulfide is, which may be the reason that the MMSG composite material is decomposed faster under the condition of low pH, and the fact that the hydrogen sulfide generation amount is higher after a trace amount of hydrogen peroxide is added is also found, which may be that the hydrogen peroxide further promotes the disassembly of the MMSG composite material. As can be seen from c, for the production of polysulfides, studies have found that a slightly acidic environment promotes the production of polysulfides, and that polysulfides also consume GSH.
Test example 6
In FIG. 6, a is 4T1 breast cancer cells and HUVEC human umbilical vein vascular endothelial normal cells with different concentrations of MoSxCell viability after incubation for 12 h/γ -MnS @ Gel-cRGD (hereinafter abbreviated as MMSGR); b is the cell viability after incubation of MMSGR with 4T1 at different concentrations for 12h under different treatment conditions.
As can be seen from FIG. 6, after 12h of incubation, the cell survival rate of HUVEC still reaches more than 80% when the concentration of MMSGR is in the range of 50 μ g/mL, and after 12h of incubation, the survival rate of 4T1 breast cancer cells is only 46% due to MMSGR, which indicates that MMSGR has a selective killing effect on cancer cells. 4T1 cells were incubated with 50. mu.g/mL MMSGR for addition of hydrogen peroxide (100. mu.M) and a 1064nm laser (0.8W cm)-2And 10min) can promote the killing effect on cells.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (10)
1. Inorganic nano MoSxThe preparation method of the/gamma-MnS composite material is characterized by comprising the following steps:
step S1, respectively adding sodium molybdate, manganese sulfate and cysteine into water to be dissolved to obtain a sodium molybdate solution, a manganese sulfate solution and a cysteine solution;
step S2, mixing and stirring the sodium molybdate solution, the manganese sulfate solution and the cysteine solution to obtain a mixed solution;
step S3. Putting the mixed solution into a reaction kettle for hydrothermal reaction, cooling to room temperature after the hydrothermal reaction is finished, centrifuging and washing to obtain the inorganic nano MoSxa/gamma-MnS heterojunction composite material.
2. The production method according to claim 1,
in the step S1, the molar ratio of the sodium molybdate to the manganese sulfate to the cysteine is 2-3: 1-2: 8-13.
3. The production method according to claim 1,
in the step S1, the mass-to-volume ratio of the sodium molybdate to the water is 0.1-0.2 g: 3-6 mL.
4. The production method according to claim 1,
in the step S1, the mass-to-volume ratio of manganese sulfate to water is 0.025-0.05 g: 3-6 mL.
5. The production method according to claim 1,
in the step S1, the mass-to-volume ratio of cysteine to water is 0.2-0.5 g: 3-8 mL.
6. The method according to claim 1, wherein in step S3, the hydrothermal reaction temperature is 160-200 ℃ and the reaction time is 20-30 h.
7. The method of claim 1, further comprising:
step S4, inorganic nano MoSxAdding the/gamma-MnS heterojunction composite material into water, adding gelatin, performing ultrasonic treatment until the gelatin is completely dissolved, stirring at room temperature, centrifuging, and washing to obtain MoSxthe/gamma-MnS @ Gel nano composite material.
8. The method of claim 1, further comprising:
s4, mixing inorganic nano MoSxAdding the/gamma-MnS heterojunction composite material into water, then adding gelatin and polypeptide cRGD, performing ultrasonic treatment until the gelatin and the polypeptide cRGD are completely dissolved, stirring at room temperature, then centrifuging, and washing to obtain MoSxthe/gamma-MnS @ Gel-cRGD nano composite material.
9. Inorganic nano MoSxa/gamma-MnS composite material, characterized in that the inorganic nano-MoSxthe/gamma-MnS composite material is prepared by the preparation method of any one of claims 1 to 8.
10. Inorganic nano MoSxUse of a/γ -MnS composite material, characterized in that the composite material prepared by the preparation method according to claims 1 to 8 or the composite material according to claim 9 is used for tumor diagnosis and treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111273552.6A CN113750235B (en) | 2021-10-29 | 2021-10-29 | Inorganic nano MoSx/gamma-MnS composite material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111273552.6A CN113750235B (en) | 2021-10-29 | 2021-10-29 | Inorganic nano MoSx/gamma-MnS composite material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113750235A true CN113750235A (en) | 2021-12-07 |
| CN113750235B CN113750235B (en) | 2022-06-10 |
Family
ID=78784581
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111273552.6A Active CN113750235B (en) | 2021-10-29 | 2021-10-29 | Inorganic nano MoSx/gamma-MnS composite material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113750235B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114229902A (en) * | 2021-12-20 | 2022-03-25 | 中原工学院 | Gamma/alpha heterogeneous-containing manganese sulfide and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU5832399A (en) * | 1998-11-12 | 2000-05-18 | Jcr Pharmaceuticals Co., Ltd. | Modulation of cell proliferative disorders by cyclic RGD |
| CN108746660A (en) * | 2018-06-11 | 2018-11-06 | 盐城工学院 | A kind of preparation method of copper gold platinum composite nano materials and its application on detection cysteine |
| CN109110815A (en) * | 2018-09-20 | 2019-01-01 | 杭州电子科技大学 | A kind of MnS-MoS2The preparation method of compound |
| CN112290018A (en) * | 2020-09-29 | 2021-01-29 | 郑州大学 | SnO (stannic oxide)2Modified MoS2Hollow microsphere sulfur-loaded positive electrode composite material and application thereof in lithium-sulfur battery |
| CN113440624A (en) * | 2021-06-29 | 2021-09-28 | 滨州医学院 | Manganese oxide-based composite nano material and preparation method thereof |
-
2021
- 2021-10-29 CN CN202111273552.6A patent/CN113750235B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU5832399A (en) * | 1998-11-12 | 2000-05-18 | Jcr Pharmaceuticals Co., Ltd. | Modulation of cell proliferative disorders by cyclic RGD |
| CN108746660A (en) * | 2018-06-11 | 2018-11-06 | 盐城工学院 | A kind of preparation method of copper gold platinum composite nano materials and its application on detection cysteine |
| CN109110815A (en) * | 2018-09-20 | 2019-01-01 | 杭州电子科技大学 | A kind of MnS-MoS2The preparation method of compound |
| CN112290018A (en) * | 2020-09-29 | 2021-01-29 | 郑州大学 | SnO (stannic oxide)2Modified MoS2Hollow microsphere sulfur-loaded positive electrode composite material and application thereof in lithium-sulfur battery |
| CN113440624A (en) * | 2021-06-29 | 2021-09-28 | 滨州医学院 | Manganese oxide-based composite nano material and preparation method thereof |
Non-Patent Citations (5)
| Title |
|---|
| N. PRIYANGA等: "Hierarchical MnS@MoS2 architectures on tea bag filter paper for flexible, sensitive, and selective non-enzymatic hydrogen peroxide sensors", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
| XIAOGUANG HAO等: "Molybdenum Dioxide (MoS2)/Gadolinium (Gd) Containing Arginine-Glycine-Aspartic Acid (RGD) Sequences as New Nano-Contrast Agent for Cancer Magnetic Resonance Imaging (MRI)", 《JOURNAL OF NANOSCIENCE AND NANOTECHNOLOGY》 * |
| XIN CAO等: "Preparation and formation process of a-MnS@MoS2 microcubes with hierarchical core/shell structure", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
| XUAN CHEN等: "MnS coupled with ultrathin MoS2 nanolayers as heterojunction photocatalyst for high photocatalytic and photoelectrochemical activities", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
| ZEINAB ZOHREBAND等: "Self-healable and flexible supramolecular gelatin/MoS2 hydrogels with molecular recognition properties", 《INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114229902A (en) * | 2021-12-20 | 2022-03-25 | 中原工学院 | Gamma/alpha heterogeneous-containing manganese sulfide and preparation method and application thereof |
| CN114229902B (en) * | 2021-12-20 | 2023-09-15 | 中原工学院 | Manganese sulfide containing gamma/alpha heterogeneous junction and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113750235B (en) | 2022-06-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Copper single-atom catalysts with photothermal performance and enhanced nanozyme activity for bacteria‐infected wound therapy | |
| Wang et al. | Recent progress of chemodynamic therapy-induced combination cancer therapy | |
| Feng et al. | Spherical mesoporous Fe-NC single-atom nanozyme for photothermal and catalytic synergistic antibacterial therapy | |
| Liu et al. | Ultra-small MoS 2 nanodots with rapid body clearance for photothermal cancer therapy | |
| Wu et al. | Bimetallic oxide Cu1. 5Mn1. 5O4 cage-like frame nanospheres with triple enzyme-like activities for bacterial-infected wound therapy | |
| Zhou et al. | MoS2-ALG-Fe/GOx hydrogel with Fenton catalytic activity for combined cancer photothermal, starvation, and chemodynamic therapy | |
| Zheng et al. | Functionalized g-C3N4 nanosheets for potential use in magnetic resonance imaging-guided sonodynamic and nitric oxide combination therapy | |
| Wang et al. | A three-in-one ZIFs-derived CuCo (O)/GOx@ PCNs hybrid cascade nanozyme for immunotherapy/enhanced starvation/photothermal therapy | |
| Gao et al. | Tumor-targeted biocatalyst with self-accelerated cascade reactions for enhanced synergistic starvation and photodynamic therapy | |
| CN105535972A (en) | C3N4 nanocomposite, preparation method and application of C3N4 nanocomposite | |
| CN113750235B (en) | Inorganic nano MoSx/gamma-MnS composite material and preparation method and application thereof | |
| Wang et al. | Degradable nanocatalyst enables antitumor/antibacterial therapy and promotion of wound healing for diabetes via self-enhanced cascading reaction | |
| CN106692970A (en) | Bismuth selenide nanocomposite material and preparation method and application thereof | |
| Li et al. | Applications and perspectives of cascade reactions in bacterial infection control | |
| CN114712500A (en) | Sensitizer for radiotherapy and application thereof | |
| Pang et al. | Aptamer modified MoS2 nanosheets application in targeted photothermal therapy for breast cancer | |
| CN113797334A (en) | Artemisinin & indocyanine green/ultrathin hydrotalcite nanosheet composite material and preparation and application thereof | |
| CN110179979A (en) | A kind of composite material and preparation method and application of the copper-based high efficiency anti-tumor of Novel vulcanization | |
| Gao et al. | Functional two-dimensional MXenes as cancer theranostic agents | |
| CN111888471A (en) | Copper sulfide photo-thermal response local release system and application thereof | |
| Chen et al. | A Cu 2+ doped mesoporous polydopamine Fenton nanoplatform for low-temperature photothermal therapy | |
| CN113648414B (en) | Metal ion coordinated carbon dot/titanium dioxide heterojunction and preparation method and application thereof | |
| Shu et al. | Photodynamic and photothermal therapy-driven synergistic cancer treatment assisted by zeolitic imidazolate framework-8: A review | |
| CN117482231A (en) | Porous copper-manganese bimetallic nano material applied to tumor immunotherapy and preparation method thereof | |
| CN112546227A (en) | Preparation method of AIPH bismuth selenide loaded nanoparticles wrapped by calcium manganese phosphide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |