CN112496336A - Preparation method of gold nanocluster with multiple optical signal channels - Google Patents
Preparation method of gold nanocluster with multiple optical signal channels Download PDFInfo
- Publication number
- CN112496336A CN112496336A CN202011304908.3A CN202011304908A CN112496336A CN 112496336 A CN112496336 A CN 112496336A CN 202011304908 A CN202011304908 A CN 202011304908A CN 112496336 A CN112496336 A CN 112496336A
- Authority
- CN
- China
- Prior art keywords
- auncs
- solution
- gold nanoclusters
- gold
- mua
- 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.)
- Pending
Links
- 239000010931 gold Substances 0.000 title claims abstract description 114
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 97
- 230000003287 optical effect Effects 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 46
- 150000002500 ions Chemical class 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 23
- 101150113720 aunc gene Proteins 0.000 claims description 70
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 62
- 239000000243 solution Substances 0.000 claims description 54
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 claims description 30
- HWYHZTIRURJOHG-UHFFFAOYSA-N luminol Chemical compound O=C1NNC(=O)C2=C1C(N)=CC=C2 HWYHZTIRURJOHG-UHFFFAOYSA-N 0.000 claims description 27
- 239000002253 acid Substances 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 20
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 238000002189 fluorescence spectrum Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000001228 spectrum Methods 0.000 claims description 6
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 5
- 239000012498 ultrapure water Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- DYAOREPNYXXCOA-UHFFFAOYSA-N 2-sulfanylundecanoic acid Chemical compound CCCCCCCCCC(S)C(O)=O DYAOREPNYXXCOA-UHFFFAOYSA-N 0.000 claims 9
- 238000001514 detection method Methods 0.000 abstract description 42
- 239000002086 nanomaterial Substances 0.000 abstract description 12
- 238000004458 analytical method Methods 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000012984 biological imaging Methods 0.000 abstract description 3
- GWOLZNVIRIHJHB-UHFFFAOYSA-N 11-mercaptoundecanoic acid Chemical compound OC(=O)CCCCCCCCCCS GWOLZNVIRIHJHB-UHFFFAOYSA-N 0.000 description 35
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000012216 screening Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- -1 aluminum ions Chemical class 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 238000004020 luminiscence type Methods 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 238000005580 one pot reaction Methods 0.000 description 4
- 102000004169 proteins and genes Human genes 0.000 description 4
- 108090000623 proteins and genes Proteins 0.000 description 4
- 208000024827 Alzheimer disease Diseases 0.000 description 3
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000002981 blocking agent Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000001186 cumulative effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 230000011664 signaling Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 101100262441 Caenorhabditis elegans rfl-1 gene Proteins 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 208000018737 Parkinson disease Diseases 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 210000004556 brain Anatomy 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 210000000987 immune system Anatomy 0.000 description 2
- NOESYZHRGYRDHS-UHFFFAOYSA-N insulin Chemical compound N1C(=O)C(NC(=O)C(CCC(N)=O)NC(=O)C(CCC(O)=O)NC(=O)C(C(C)C)NC(=O)C(NC(=O)CN)C(C)CC)CSSCC(C(NC(CO)C(=O)NC(CC(C)C)C(=O)NC(CC=2C=CC(O)=CC=2)C(=O)NC(CCC(N)=O)C(=O)NC(CC(C)C)C(=O)NC(CCC(O)=O)C(=O)NC(CC(N)=O)C(=O)NC(CC=2C=CC(O)=CC=2)C(=O)NC(CSSCC(NC(=O)C(C(C)C)NC(=O)C(CC(C)C)NC(=O)C(CC=2C=CC(O)=CC=2)NC(=O)C(CC(C)C)NC(=O)C(C)NC(=O)C(CCC(O)=O)NC(=O)C(C(C)C)NC(=O)C(CC(C)C)NC(=O)C(CC=2NC=NC=2)NC(=O)C(CO)NC(=O)CNC2=O)C(=O)NCC(=O)NC(CCC(O)=O)C(=O)NC(CCCNC(N)=N)C(=O)NCC(=O)NC(CC=3C=CC=CC=3)C(=O)NC(CC=3C=CC=CC=3)C(=O)NC(CC=3C=CC(O)=CC=3)C(=O)NC(C(C)O)C(=O)N3C(CCC3)C(=O)NC(CCCCN)C(=O)NC(C)C(O)=O)C(=O)NC(CC(N)=O)C(O)=O)=O)NC(=O)C(C(C)CC)NC(=O)C(CO)NC(=O)C(C(C)O)NC(=O)C1CSSCC2NC(=O)C(CC(C)C)NC(=O)C(NC(=O)C(CCC(N)=O)NC(=O)C(CC(N)=O)NC(=O)C(NC(=O)C(N)CC=1C=CC=CC=1)C(C)C)CC1=CN=CN1 NOESYZHRGYRDHS-UHFFFAOYSA-N 0.000 description 2
- 238000000513 principal component analysis Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 108091023037 Aptamer Proteins 0.000 description 1
- 208000006820 Arthralgia Diseases 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 108010075016 Ceruloplasmin Proteins 0.000 description 1
- 102100023321 Ceruloplasmin Human genes 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 206010012735 Diarrhoea Diseases 0.000 description 1
- 108010043121 Green Fluorescent Proteins Proteins 0.000 description 1
- 102000004144 Green Fluorescent Proteins Human genes 0.000 description 1
- 102000001554 Hemoglobins Human genes 0.000 description 1
- 108010054147 Hemoglobins Proteins 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- 208000003367 Hypopigmentation Diseases 0.000 description 1
- 102000004877 Insulin Human genes 0.000 description 1
- 108090001061 Insulin Proteins 0.000 description 1
- 241000124008 Mammalia Species 0.000 description 1
- 206010027476 Metastases Diseases 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 206010039966 Senile dementia Diseases 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 210000001744 T-lymphocyte Anatomy 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 102000003425 Tyrosinase Human genes 0.000 description 1
- 108060008724 Tyrosinase Proteins 0.000 description 1
- 229930003779 Vitamin B12 Natural products 0.000 description 1
- 229930003316 Vitamin D Natural products 0.000 description 1
- QYSXJUFSXHHAJI-XFEUOLMDSA-N Vitamin D3 Natural products C1(/[C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@H](C)CCCC(C)C)=C/C=C1\C[C@@H](O)CCC1=C QYSXJUFSXHHAJI-XFEUOLMDSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 208000007502 anemia Diseases 0.000 description 1
- 239000000427 antigen Substances 0.000 description 1
- 102000036639 antigens Human genes 0.000 description 1
- 108091007433 antigens Proteins 0.000 description 1
- 230000006907 apoptotic process Effects 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000037396 body weight Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000003759 clinical diagnosis Methods 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- FDJOLVPMNUYSCM-WZHZPDAFSA-L cobalt(3+);[(2r,3s,4r,5s)-5-(5,6-dimethylbenzimidazol-1-yl)-4-hydroxy-2-(hydroxymethyl)oxolan-3-yl] [(2r)-1-[3-[(1r,2r,3r,4z,7s,9z,12s,13s,14z,17s,18s,19r)-2,13,18-tris(2-amino-2-oxoethyl)-7,12,17-tris(3-amino-3-oxopropyl)-3,5,8,8,13,15,18,19-octamethyl-2 Chemical compound [Co+3].N#[C-].N([C@@H]([C@]1(C)[N-]\C([C@H]([C@@]1(CC(N)=O)C)CCC(N)=O)=C(\C)/C1=N/C([C@H]([C@@]1(CC(N)=O)C)CCC(N)=O)=C\C1=N\C([C@H](C1(C)C)CCC(N)=O)=C/1C)[C@@H]2CC(N)=O)=C\1[C@]2(C)CCC(=O)NC[C@@H](C)OP([O-])(=O)O[C@H]1[C@@H](O)[C@@H](N2C3=CC(C)=C(C)C=C3N=C2)O[C@@H]1CO FDJOLVPMNUYSCM-WZHZPDAFSA-L 0.000 description 1
- 210000002808 connective tissue Anatomy 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000000412 dendrimer Substances 0.000 description 1
- 229920000736 dendritic polymer Polymers 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000002526 effect on cardiovascular system Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 206010015037 epilepsy Diseases 0.000 description 1
- 210000003743 erythrocyte Anatomy 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 238000001917 fluorescence detection Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 230000002496 gastric effect Effects 0.000 description 1
- 210000001035 gastrointestinal tract Anatomy 0.000 description 1
- 239000005090 green fluorescent protein Substances 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000003425 hypopigmentation Effects 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000003018 immunoassay Methods 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 229940125396 insulin Drugs 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 230000010438 iron metabolism Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 210000001165 lymph node Anatomy 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000008897 memory decline Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000009401 metastasis Effects 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- 239000002090 nanochannel Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000001991 pathophysiological effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000019491 signal transduction Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 210000003491 skin Anatomy 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 210000001685 thyroid gland Anatomy 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 210000004881 tumor cell Anatomy 0.000 description 1
- 235000019163 vitamin B12 Nutrition 0.000 description 1
- 239000011715 vitamin B12 Substances 0.000 description 1
- 235000019166 vitamin D Nutrition 0.000 description 1
- 239000011710 vitamin D Substances 0.000 description 1
- 150000003710 vitamin D derivatives Chemical class 0.000 description 1
- 229940046008 vitamin d Drugs 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/0553—Complex form nanoparticles, e.g. prism, pyramid, octahedron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/76—Chemiluminescence; Bioluminescence
Abstract
The invention discloses a preparation method of gold nanoclusters with multiple optical signal channels, which belongs to the technical field of functionalized nano material detection, and relates to gold nanoclusters for selectively distinguishing multiple optical signals for detecting multiple heavy metal ions. The method has the advantages of simplicity, rapidness and low price, and the gold nanoclusters synthesized by the method are uniform in size and have good chemiluminescence and fluorescence characteristics. The gold nanoclusters prepared by the method can be used for selectively distinguishing various heavy metal ions. The gold nanocluster with the multiple optical signal channels has wide application prospects in the fields of biological analysis and biological imaging.
Description
Technical Field
The invention relates to the field of gold nanoclusters, in particular to a gold nanocluster with multiple optical signal channels, a preparation method of the gold nanocluster and application of the gold nanocluster in selective detection of heavy metal ions.
Background
Metal nanoclusters having luminescence properties, such as gold and silver nanoclusters, are very close in size to the fermi wavelength of electrons and thus may exhibit characteristics similar to discrete electronic states of molecules. The ultrafine gold nanoclusters are composed of several gold atoms, have phosphorescence and fluorescence properties related to the size, and due to good light stability and biocompatibility, the gold nanoclusters with the luminescence property are deeply applied to the aspects of in vivo and in vitro imaging, metal ion sensing, biosensor construction and the like in recent years. In the past decades, many methods have been developed to synthesize gold nanoclusters, for example, gold nanoclusters using polyamide dendrimers as protective agents may have various emission wavelengths from far ultraviolet to near infrared.
The chemical nose/tongue detection strategy simulates the olfactory system of mammals, and the chemical nose/tongue detection strategy is developed rapidly since the application of nano materials in the field. A chemical nasal/lingual detection sensor is generally defined as an array detection sensing system that can produce different responses to different target analytes. The existing detection strategy establishes an array detection method based on green fluorescent protein and different functionalized nano materials, and can successfully distinguish and identify different proteins. However, the ability of the array detection sensor to identify and distinguish is closely related to the number of sensing elements. Most of the reported array detection sensing strategies are based on a single signal pathway, such as a fluorescent signal. If more signal paths can be introduced, the sensing capability of the sensor should be improved.
One solution is to design a nano-channel with multiple optical signal channelsRice material. A number of nanomaterials and compounds have been developed with a variety of signals and are referred to as molecular or nano-material laboratories. Such as: carbon nitride nano material (g-C) with multiple signal channels3N4) The photoluminescence signal, rayleigh scattering signal and uv-visible signal are used to distinguish the proteins. However, these array detection strategies extract only one signal parameter from each optical signal, which increases the complexity of detection, the detection time, and wastes signal resources. Another way to enhance the detection of the array is to extract multiple valid parameters from a single signal source.
Heavy metal contamination is a very serious problem. The source range of heavy metal ions is wide, but the analysis is carried out from the actual source channel, the heavy metal ions in the water mainly come from chemical industry, printing textile, inorganic pigment and the like, and meanwhile, domestic sewage, mining wastewater and the like in cities are also contained, and when the sewage is discharged into the environment and is spread through a food chain, the influence on animals and plants is more serious. Wherein an excessively high concentration of Al3+The ions can cause damage to the immune system and the central nervous system of a human body, and cause red blood cell hypopigmentation anemia, reduction of biological enzyme activity, cell decay and the like, so that serious diseases such as Alzheimer disease, Parkinson disease, senile dementia and the like are caused: when Al is present in human brain tissue3+When the ion deposition is excessive, the damage to the brain can be caused, and the symptoms of low intelligence, memory decline, slow action and the like are presented; in addition, when the concentration of aluminum ions in human body is too high, the absorption of calcium, phosphorus and other elements and vitamin D in human body is inhibited, and joint pain and skeleton softness are seriously caused. According to the regulations of the world health organization of the United nations, the concentration of aluminum ions in drinking water must not exceed 200mg/L, and the maximum amount of aluminum ingested per week per 1Kg of human body weight must not exceed 7 mg. The cobalt compound is widely distributed in nature, generally, the cobalt content in the soil is 0.05-65.00 mg kg-1Median value of 8mg kg-1In human life activities, cobalt is an important component of vitamin B12 and participates in many biochemical reactions. However, excessive Co-uptakeThe compounds have been shown to have adverse effects on skin, lung, thyroid, etc. Studies have shown that co (ii) implanted in artificial joints in humans can transfer to the internal environment of the human body, inducing apoptosis, and thereby inhibiting T lymphocyte expansion, which researchers have observed in hip aspirates and regional lymph nodes where patients are implanted in artificial joints. The concentration of cobalt ions in domestic water is clearly regulated in many countries, for example, the maximum concentration of cobalt in domestic water supply source proposed by China is 0.02mg L-1(ii) a Chromium is a necessary trace element for the growth of human bodies, animals and plants, has an important effect on maintaining the normal functions of the human bodies, is an indispensable auxiliary component of insulin, can be absorbed by gastrointestinal digestive tracts when entering the human bodies through water and food, and has the effects of carcinogenesis, teratogenesis and mutagenesis after long-term accumulation. In organisms, copper element is a catalytic auxiliary factor of a plurality of metalloenzymes and proteins, can participate in a plurality of oxidation-reduction reactions, and has important effects on the metabolism process of organisms, such as Cu-Zn-SOD, DA-beta-hydroxylase, tyrosinase, ceruloplasmin and the like; copper can participate in iron metabolism, which is beneficial to the synthesis of hemoglobin; can affect the generation and the metastasis of the tumor and inhibit the proliferation of tumor cells; plays a fundamental role in the formation of bone, nervous system, cardiovascular and connective tissue in the field of pathophysiological studies, Zn2+Play an irreplaceable role in the catalysis and conversion processes of biological enzymes. When zinc in a human body is deficient, the zinc can cause the disturbance of the immune system of the human body, diarrhea, epilepsy and the like; if the zinc is excessively ingested, the human body can be harmed, and various diseases can be caused, such as Parkinson's disease, Alzheimer's disease and the like3+，Co2+，Cr3+，Cu2+And Zn2+And (3) a detection method.
The prior art luminol modified gold nano-material (CN102191034A, CN101900723A, CN102021226A, CN104371705A and the like) has the particle size of more than or equal to 10nm, has chemiluminescence property due to the modification of the luminol, does not have fluorescence property, is applied to pesticide detection, immunoassay such as detection of antibodies, antigens or proteins and detection of nucleic acids such as DNA, RNA and aptamer molecules, and is not applied to detection of heavy metals.
In addition, in the prior art, gold nanoclusters are used for detecting heavy metals, but only one signal in fluorescence or chemiluminescence can be generally used for detecting single metal ions, and more than two different types of heavy metal ions cannot be detected simultaneously.
The chemiluminescence and fluorescence-based analysis technology has the advantages of simple instrument and device, rapid analysis, high sensitivity, wide linear range and the like, and is widely applied to the fields of clinical diagnosis, food safety, environmental monitoring and the like. In the traditional detection strategy, chemiluminescence and fluorescence spectrum also only extract a valid signal to detect the target. In fact, other effective parameters in the spectrum are ignored and not effectively utilized, such as chemiluminescence signals at different times, integrated values of the luminescence signals, and fluorescence signals at different peak positions.
There is an urgent need to develop a gold nanocluster prepared by a one-pot method and having multiple optical signal paths, wherein the gold nanocluster simultaneously has a chemiluminescent signal and a fluorescent signal so as to construct a heavy metal ion sensing detection array, and the detection array can successfully distinguish different heavy metal ions and different metal ion concentrations.
Disclosure of Invention
The invention aims to provide a double-signal functionalized gold nanocluster with chemiluminescence and fluorescence signals, a preparation method thereof and application thereof in heavy metal ion array detection and analysis, wherein the content comprises the following aspects:
gold nanoclusters AuNCs having a chemiluminescent and fluorescent multiple light signal channel with luminol and undecament undecanoic acid (MUA) attached to their surfaces are provided, having a particle size of less than about 10 nm.
The gold nanoclusters AuNCs are formed by using 11-mercaptoundecanoic acid (MUA) as a blocking agent and chloroauric acid to form Au (I) -thiol complexes, and introducing luminol as a reducing agent to reduce the Au (I) -thiol complexes.
The particle size of the gold nanoclusters AuNCs is less than about 10nm, or less than about 5nm, or less than about 3nm, and preferably the particle size is about 2nm, and the gold nanoclusters AuNCs have both fluorescence and chemiluminescence properties.
The preparation method of the gold nanoclusters AuNCs comprises the following steps: (1) dissolving undecamydryl undecanoic acid (MUA) in a NaOH solution, and mixing with a chloroauric acid aqueous solution under a stirring state to obtain a mixed solution;
(2) dropwise adding NaOH under the stirring state until the solution becomes clear, and stirring the solution to obtain an Au (I) -thiol complex formed by MUA and gold;
(3) and (3) heating the solution under a stirring state, adding the luminol aqueous solution into the solution obtained in the step (2), and continuously stirring to obtain the gold nanocluster AuNCs.
The amount of the substance of the undecamydryl undecanoic acid (MUA) in the undecamydryl undecanoic acid (MUA) solution in the step (1) is 3 to 6 times of the amount of the substance of the chloroauric acid in the aqueous chloroauric acid solution, and preferably the amount of the substance of the undecamydryl undecanoic acid (MUA) in the undecamydryl undecanoic acid (MUA) solution is 4 times of the amount of the substance of the chloroauric acid in the aqueous chloroauric acid solution.
And (3) stirring the solution in the step (2) for 10-30 minutes to obtain an Au (I) -thiol complex formed by the undecamydryl undecanoic acid (MUA) and the gold, and preferably stirring the solution for 20 minutes to obtain an Au (I) -thiol complex formed by the undecamydryl undecanoic acid (MUA) and the gold.
In the step (3), the solution is heated to 20-120 ℃, preferably 50-100 ℃, and more preferably 60 ℃ under the stirring state, the amount of the luminol in the luminol aqueous solution is 0.40-2.67 times of the amount of the chloroauric acid in the chloroauric acid aqueous solution in the step (1), the continuous stirring time is preferably 5-24h, more preferably 7-10h, and more preferably 8 h.
Provided is gold nanoclusters (AuNCs) with a chemiluminescent and fluorescent multi-optical signal channel, wherein the gold nanoclusters are formed by an Au (I) -thiol complex by using 11-mercaptoundecanoic acid (MUA) as a blocking agent and Au (I), and then luminol is introduced as a reducing agent to reduce the Au (I) -thiol complex to form the AuNC, is connected to the surface of the gold nanoclusters through covalent bonds Au-N, and has a particle size of about 2.0 +/-0.5 nm.
The gold nanoclusters AuNCs have a chemiluminescence characteristic, and the gold nanoclusters AuNCs react with hydrogen peroxide to generate chemiluminescence.
The gold nanoclusters AuNCs have fluorescence characteristics, and have fluorescence emission peaks at 424nm and 598 nm.
The preparation method of the gold nanocluster AuNCs comprises the following steps: (1) dissolving 11-mercaptoundecanoic acid (MUA) in NaOH solution, and mixing with chloroauric acid aqueous solution under stirring to obtain mixed solution; the amount of MUA species in the aqueous MUA solution is 4 times the amount of chloroauric acid species in the aqueous chloroauric acid solution;
(2) dropwise adding NaOH under stirring until the solution becomes clear, and stirring the solution for 20 minutes to obtain an Au (I) -thiol complex formed by 11-mercaptoundecanoic acid (MUA) and gold;
(3) heating the solution to 60 ℃ under the stirring state, adding the luminol water solution into the solution obtained in the step (2), and continuously stirring for 8 hours to obtain gold nanoclusters, namely AuNCs; the amount of the luminol substance in the luminol water solution is 0.40-2.67 times that of the chloroauric acid substance in the chloroauric acid water solution in the step (1).
The method further comprises the step of purifying the functionalized gold nanoclusters by centrifugation.
The functionalized gold nanoclusters may be centrifuged under the following conditions: the initially synthesized gold nanoclusters are mixed with acetonitrile in a volume ratio of 1: 2 and centrifuged at 12000rpm for 5 minutes, and then the precipitate is dissolved with distilled or deionized water or ultrapure water.
The method for distinguishing the array of the heavy metal ions is developed based on the functionalized gold nanoclusters.
The heavy metal ions are Al3+，Co2+，Cr3+，Cu2+And Zn2+And the gold nanoclusters are selectively distinguished through different influences of the heavy metal ions on chemiluminescence spectrums and fluorescence spectrums of the gold nanoclusters AuNCs.
The invention develops a gold nanocluster with a multi-optical signal channel prepared by a one-pot method, and the gold nanocluster has a chemiluminescent signal and a fluorescent signal at the same time. The AuNCs prepared are analyzed by a high-resolution transmission electron microscope and X photoelectron spectroscopy, and chemiluminescence and fluorescence signals of the AuNCs are researched. In order to fully utilize the chemiluminescence and fluorescence signal channels, five effective parameters are extracted from the chemiluminescence spectrum and the fluorescence spectrum and are used for constructing a heavy metal ion sensing detection array. The detection array can successfully distinguish different heavy metal ions and different metal ion concentrations.
Compared with the prior art, the invention has the following advantages:
(1) the gold nanocluster has the size of below 10nm, and the size of below 10nm, preferably 2nm, is obtained by using 11-mercaptoundecanoic acid (MUA) as a stabilizer, so that a chemiluminescence signal and a fluorescence signal are simultaneously provided, a heavy metal ion sensing detection array can be constructed, multiple heavy metal ions can be simultaneously selected and distinguished, and the heavy metal ions are Al3+，Co2+，Cr3+，Cu2+And Zn2+And e.g. Hg2+，Pb2+The equal-heavy metal ions are obviously distinguished on signals, the gold nanocluster with the multiple optical signal channels has wide application prospects in the fields of biological analysis and biological imaging, the defect that a plurality of different detection reagents need to be replaced in actual detection application is overcome, and the instantaneity and the convenience are improved.
(2) The gold nanoclusters synthesized by the one-pot method are uniform in size and have good chemiluminescence and fluorescence characteristics, and the method has the advantages of being simple, rapid and low in price.
(3) The gold nanoclusters can simultaneously select and distinguish various heavy metal ions through different influences of the heavy metal ions on chemiluminescence spectrums and fluorescence spectrums of the gold nanoclusters AuNCs.
Drawings
FIG. 1 is a high-resolution transmission electron microscope of gold nanoclusters AuNCs with multiple optical signal channels for chemiluminescence and fluorescence;
FIG. 2 is an X-ray photoelectron spectrum of gold nanoclusters AuNCs having multiple optical signal channels for chemiluminescence and fluorescence; FIG. 3 is a graph of the relative chemiluminescence kinetics of gold nanoclusters AuNCs with multiple optical signal channels for chemiluminescence and fluorescence;
FIG. 4 is a conditional screening of gold nanoclusters AuNCs having multiple optical signal channels for chemiluminescence and fluorescence, wherein FIG. 4A is a synthesis conditional screening;
FIG. 4B is a screening of the concentration of sodium hydroxide in the assay conditions; FIG. 4C is a screening of the concentration of hydrogen peroxide in the assay conditions;
FIG. 5 is a fluorescence signal characteristic diagram of gold nanoclusters AuNCs having multiple optical signal channels for chemiluminescence and fluorescence;
FIG. 6 is Al3+，Co2+，Cr3+，Cu2+，Hg2+，Pb2+And Zn2+The chemiluminescence and fluorescence signal influence on gold nanocluster AuNCs with a multi-optical signal channel of chemiluminescence and fluorescence.
FIG. 7 shows Al3+，Co2+，Cr3+，Cu2+，Hg2+，Pb2+And Zn2+Array detection of the images at a single concentration;
FIG. 8 shows Al3+，Co2+，Cr3+，Cu2+，Hg2+，Pb2+And Zn2+The images were detected on an array at different concentrations.
Detailed Description
Example 1 Synthesis of gold nanoclusters AuNCs with multiple optical signaling channels for chemiluminescence and fluorescence.
And (3) reagent sources: chloroauric acid, acetonitrile, heavy metal ions, and hydrogen peroxide were obtained from Shanghai reagent, luminol was obtained from TCI reagent, and 11-mercaptoundecanoic acid (MUA) was obtained from Anyiji reagent.
The AuNCs are prepared by the following steps: 0.0131g of 11-mercaptoundecanoic acid (MUA) was dissolved in 18mL of ultrapure water containing NaOH, followed by addition of 10mM of 1.5mL of chloroauric acid solution, followed by dropwise addition of NaOH solution to bring the originally turbid solution into a clear state. After the solution was stirred for 20 minutes, 0.9mL of 10mM luminol solution was added dropwise and the mixture was heated and stirred at 60 deg.C for 8 hours. Finally the excess was separated by adding acetonitrile (mixed with nanomaterial at a volume ratio of 2: 1) and centrifuging (12000 rpm). The prepared AuNCs were redispersed in water and stored at 4 degrees Celsius for use.
The characterization is shown in FIG. 1: the high-resolution transmission electron microscope shows that the 11-mercaptoundecanoic acid (MUA) is modified on the surface of AuNCs, so that the aggregation of gold nanoclusters is effectively inhibited, and the dispersibility of the AuNCs is good. The size distribution range of the gold nanoclusters is relatively small, and the size of the gold nanoclusters is 2.0 +/-0.5 nm.
Example 2 Synthesis of gold nanoclusters AuNCs with multiple optical signaling channels for chemiluminescence and fluorescence.
The AuNCs are prepared by the following steps: 0.0131g of 11-mercaptoundecanoic acid (MUA) was dissolved in 18mL of ultrapure water containing NaOH, followed by addition of 10mM of 1.5mL of chloroauric acid solution, followed by dropwise addition of NaOH solution to bring the originally turbid solution into a clear state. After the solution was stirred for 20 minutes, 0.9mL of 10mM luminol solution was added dropwise and the mixture was heated and stirred at 100 deg.C for 5.5 hours. Finally the excess was separated by adding acetonitrile (mixed with nanomaterial at a volume ratio of 2: 1) and centrifuging (12000 rpm). The prepared AuNCs were redispersed in water and stored at 4 degrees Celsius for use.
Example 3 Synthesis of gold nanoclusters AuNCs with multiple optical signaling channels for chemiluminescence and fluorescence.
The AuNCs are prepared by the following steps: 0.0131g of 11-mercaptoundecanoic acid (MUA) was dissolved in 18mL of ultrapure water containing NaOH, followed by addition of 10mM of 1.5mL of chloroauric acid solution, followed by dropwise addition of NaOH solution to bring the originally turbid solution into a clear state. After the solution was stirred for 20 minutes, 0.9mL of 10mM luminol solution was added dropwise and the mixture was heated and stirred at 80 deg.C for 24 hours. Finally the excess was separated by adding acetonitrile (mixed with nanomaterial at a volume ratio of 2: 1) and centrifuging (12000 rpm). The prepared AuNCs were redispersed in water and stored at 4 degrees Celsius for use.
The invention makes X-ray photoelectron spectrum to research the valence state of gold atom in the functional gold nanocluster. FIG. 2 shows an X-ray photoelectron spectrum of functionalized Au 4f of gold nanocluster7/2The binding energy was 84.3eV, which is between the binding energy of 84.0eV for Au (0) and 85.1eV for Au (i), indicating that Au (0) and Au (i) coexist in the functionalized gold nanoclusters. Au 4f7/2And Au 4f5/2The difference of the spin-orbit splitting energy level of the compound is 3.7eV, which is completely consistent with the report of the prior literature. Because the surface of the gold cluster is functionalized with the undecamcapto undecanoic acid and the luminol, the energy level peak of C1s can be seen to be split into four peaks of C1, C2, C3 and C4, which respectively correspond to-CH-, -C-NH-, -CO-NH-and-COO-groups, and the peak of C1 is particularly obvious due to the existence of the undecamcapto undecanoic acid. The 1s peak of N is divided into two portions, 400.0eV and 400.8eV respectively, corresponding to the-N-C-and-N-CO-groups of luminol respectively.
To investigate the chemiluminescent performance of the AuNCs prepared, we will use 150mL of 5mM H2O2Solution (c)NaOH0.1M) was injected into 150mL of the prepared AuNCs solution, and a chemiluminescent signal was measured by an RFL-1 type photometer. Under the same detection condition, the chemiluminescence properties of the luminol functionalized gold nano-material and the mixture of the gold nanocluster and the luminol solution are detected, and are compared with the chemiluminescence dynamics curve of AuNCs, and the result shows that the chemiluminescence properties of AuNCs are optimal, which is probably the synergistic catalytic effect of MUA and the gold nanocluster on a luminol hydrogen peroxide chemiluminescence system. In previous work, it has been demonstrated that the enhanced and catalytic mechanism of chemiluminescence is associated with the production of oxygen radicals (including OH)·，O2 ·-And other derivatives of radicalsBiological), gold nanomaterials can promote the generation of electron transfer radicals during chemical reactions. Thus, under the catalytic action of gold nanoclusters, H2O2Can be cleaved into two OH radicals which can react with HO2-The luminol anion, thereby promoting O2 ·-And the formation of MS-AuNCs functionalized luminol free radicals, thereby accelerating the chemiluminescent reaction. In addition, early studies have shown that carboxyl group-containing substances such as amino acids and phenolic compounds can enhance luminol-H2O2-Co2+The chemiluminescence intensity of the system. Thus, the enhancement of chemiluminescence may be attributed to the carboxyl groups and O on the MUA molecule2 ·-By reaction of formed-CO4 ·2-Related, to-CO4 ·2-Can react with the luminol to promote the generation of luminol free radicals, thereby enhancing the chemiluminescence intensity. Therefore, the good chemiluminescence of AuNCs and hydrogen peroxide systems can be attributed to the promotion of HO during chemical reaction by MUA and gold nanoclusters·，O2·-and-CO4 ·2-And the gold nanoclusters, as a nano-sized reaction platform, can also promote the generation of radicals for a chemiluminescent reaction, thereby obtaining strong chemiluminescence.
Example 4.
In order to obtain the best chemiluminescence effect, the preparation conditions are optimized, as shown in fig. 4A, the chemiluminescence performance of AuNCs begins to increase along with the increase of the reaction time and the reaction temperature, and the best chemiluminescence effect is obtained at the reaction temperature of 60 ℃ and the reaction time of 8 h.
Test conditions for chemiluminescence:
the chemiluminescent signal was detected on an RFL-1 type luminescence detector (Siamelimei, China) by mixing 150. mu.L of the gold nanoclusters with 150. mu.L of 5mM H2O2(0.1M NaOH) mixing produced a chemiluminescent signal. For array sensing detection, gold nanoclusters and different heavy metal ions are mixed in a volume ratio of 9: 1 at corresponding concentrations respectively, incubated at room temperature for 10 minutes, and 150 μ L of the mixture is injected into quartz chemiluminescence detectionIn the cell, 150. mu.L of 5mM H was then added2O2(0.1M NaOH) was injected into the test cell and the chemiluminescent signal was recorded.
Test conditions for fluorescence:
the fluorescence signal was detected on an F-7000 type fluorescence detector (Xe lamp 150W, Hitachi, light source) with an excitation wavelength of 290nm, by mixing gold nanoclusters and different heavy metal ions at respective concentrations in a volume ratio of 9: 1, incubating at room temperature for 10 minutes, injecting 150. mu.L of the above mixture into a quartz fluorescence detection cell, and recording the fluorescence signal.
We also optimized the chemiluminescent reaction conditions, as shown in FIGS. 4B and 4C, with the intensity of chemiluminescence being dependent on H2O2The NaOH concentration of the solution increased significantly, and when the NaOH concentration was 0.1M, the best chemiluminescence was obtained, after which continued increase of the NaOH concentration resulted in a decrease in the chemiluminescence intensity, probably due to the initial increase in pH promoting H2O2When the NaOH concentration exceeds 0.1M, the blocking agent MUA starts to fall off from the AuNCs surface, leading to aggregation of AuNCs, resulting in a decrease in the chemiluminescence intensity. When H is present2O2The increase in concentration from 0.5mM to 5mM resulted in a significant increase in chemiluminescence intensity, after which continued increase resulted in a decrease in chemiluminescence intensity. Thus, the optimal chemiluminescent reaction condition is 5mM H2O2(0.1M，NaOH)。
The fluorescence properties of AuNCs are shown in FIG. 5, and the orange fluorescence of AuNCs solution is visible to the naked eye (corresponding to an emission peak at 598 nm). The emission peak at 424nm corresponds to the AuNCs surface-modified luminol. As the excitation peak increases from 270nm to 350nm, the emission peak position of AuNCs hardly shifts, which is likely because the synthesized AuNCs is a single species and thus the excitation spectrum and the emission spectrum are both fixed. The fluorescence intensity at 598nm reaches a maximum when the excitation wavelength is 290 nm.
Example 5 Selective Distinguishing detection of heavy Metal ions
The detection method comprises the following steps: in order to explore the application of the AuNCs material in the aspect of heavy metal ion detection arrays,we investigated the effect of different heavy metal ions on the chemiluminescent and fluorescent signals of AuNCs. Detection of Fe3+、Sn2+、Ni2+、Mn2+、Ag+、Fe2+、Al3+，Co2+，Cr3+，Cu2+，Hg2+，Pb2+And Zn2+And 7 heavy metal ions with relatively strong chemiluminescence signals and fluorescence signals are preliminarily screened from the heavy metal ions as detection targets (namely Fe)3+、Sn2+、Ni2+、Mn2+、Ag+、Fe2+Weak signal) including Al3 +，Co2+，Cr3+，Cu2+，Hg2+，Pb2+And Zn2+And screening again to find Al3+，Co2+，Cr3+，Cu2+And Zn2+Can be mixed with Hg2+，Pb2+And (4) directly distinguishing. To fully utilize the optical signal channel of AuNCs, we extracted 5 effective parameters from the chemiluminescence spectrum and the fluorescence spectrum, and we studied the effects of heavy metal ions on the cumulative intensity of chemiluminescence 60s, peak intensity, intensity at 60s, intensity of fluorescence at 598nm, and intensity value of fluorescence at 424 nm. After adding different heavy metal ions to AuNCs respectively, AuNCs produce different signal changes under the influence of the heavy metal ions, as shown in FIG. 6. Therefore, the five parameters of the cumulative intensity of chemiluminescence 60s, the peak intensity, the intensity at 60s, the intensity of fluorescence at 598nm and the intensity value of fluorescence at 424nm are used for establishing a heavy metal ion sensing detection array.
The detection results are shown in fig. 7: principal component analysis is a means of processing complex, high-dimensional data, and can simplify data while preserving data trend characteristics. Therefore, it is an effective tool for processing experimental data, and can be used to process the signal response data generated by heavy metal ions to AuNCs, including the cumulative intensity of chemiluminescence 60s, peak intensity, intensity at 60s, intensity of fluorescence at 598nm, and intensity value of fluorescence at 424 nm. Each heavy metal ion was measured three times to obtain five characteristic signals of chemiluminescence and fluorescence of AuNCs, and then principal component analysis was performed on the data. The first three main classified data obtained by analysis are used for establishing a three-dimensional data chart, each point represents the response result of the heavy metal ion sample to the detection array, and the result shows that the detection array can successfully distinguish different heavy metal ions.
We also investigated the discrimination of heavy metal ions at different concentrations. It was found that 7 heavy metal ions were well differentiated in the detection sensor array at two different concentrations (1. mu.g/mL and 0.5. mu.g/mL). The results are shown in FIG. 8, from which FIG. 8 we can distinguish Al at the same time3+，Co2+，Cr3+，Cu2+And Zn2+And the respective concentrations thereof were determined.
In the invention, a mild one-pot method is provided for preparing AuNCs with the size of 2.0 +/-0.5 nm. The synthesized AuNCs have excellent chemiluminescence and fluorescence properties, and based on chemiluminescence and fluorescence signals of AuNCs materials, a detection array sensing method capable of distinguishing different heavy metal ions and different concentrations of heavy metal ions is established. The work synthesizes a multi-signal functionalized gold nanocluster for the first time, and the multi-signal functionalized gold nanocluster has potential application prospects in the fields of biological analysis and biological imaging.
Claims (9)
1. A preparation method of gold nanocluster AuNCs with a chemiluminescent and fluorescent multi-optical signal channel is characterized by comprising the following steps: (1) dissolving undecamydryl undecanoic acid (MUA) in a NaOH solution, and mixing with a chloroauric acid aqueous solution under a stirring state to obtain a mixed solution;
(2) dropwise adding NaOH under stirring state until the solution becomes clear, and stirring the solution to obtain an Au (I) -mercaptan complex formed by undecamyl Mercapto Undecanoic Acid (MUA) and gold;
(3) heating the solution under a stirring state, adding a luminol aqueous solution into the solution obtained in the step (2), and continuously stirring to obtain gold nanocluster AuNCs; the gold nanoclusters AuNCs have luminol and undecamyl undecanoic acid (MUA) attached to their surfaces, and their particle size is less than about 10 nm.
2. The method for preparing gold nanoclusters AuNCs as claimed in claim 2, wherein the amount of the substance of undecamydryl undecanoic acid (MUA) in the undecamydryl undecanoic acid (MUA) solution in the step (1) is 3 to 6 times the amount of the substance of chloroauric acid in the aqueous chloroauric acid solution, and the particle size thereof is less than about 10nm, and preferably the amount of the substance of undecamydryl undecanoic acid (MUA) in the undecamydryl acid (MUA) solution is 4 times the amount of the substance of chloroauric acid in the aqueous chloroauric acid solution, which has fluorescence and chemiluminescence characteristics.
3. The method for preparing gold nanoclusters AuNCs according to claim 2, wherein said gold nanoclusters AuNCs have a particle size of less than about 3nm, preferably a particle size of about 2 nm.
4. The method for preparing gold nanoclusters (AuNCs) as claimed in claim 1, wherein the solution in the step (2) is stirred for 10-30 minutes to obtain Au (I) -thiol complex formed by undecamydrylundecanoic acid (MUA) and gold, preferably for 20 minutes.
5. The method for preparing gold nanoclusters (AuNCs) as claimed in claim 1, wherein in the step (3), the solution is heated to 60 ℃ under stirring, and the amount of the luminol substance in the luminol aqueous solution is 0.40-2.67 times the amount of the chloroauric acid substance in the chloroauric acid aqueous solution in the step (1).
6. The method for preparing gold nanoclusters, AuNCs, as claimed in claim 5, further comprising the step of purifying said functionalized gold nanoclusters by centrifugation: the initially synthesized gold nanoclusters are mixed with acetonitrile in a volume ratio of 1: 2 and centrifuged at 12000rpm for 5 minutes, and then the precipitate is dissolved with distilled or deionized water or ultrapure water.
7. The method for preparing gold nanoclusters AuNCs according to claim 1, wherein the gold nanoclusters AuNCs can selectively distinguish and detect heavy metal ions simultaneously.
8. The method of claim 7, wherein the heavy metal ions are Al3+，Co2+，Cr3+，Cu2+And Zn2+。
9. The method for preparing gold nanoclusters AuNCs according to claim 8, wherein the method is selectively distinguished by different influences of the heavy metal ions on the chemiluminescence spectrum and the fluorescence spectrum of the gold nanoclusters AuNCs of multiple optical signals.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011304908.3A CN112496336A (en) | 2020-11-13 | 2020-11-13 | Preparation method of gold nanocluster with multiple optical signal channels |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011304908.3A CN112496336A (en) | 2020-11-13 | 2020-11-13 | Preparation method of gold nanocluster with multiple optical signal channels |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112496336A true CN112496336A (en) | 2021-03-16 |
Family
ID=74958852
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011304908.3A Pending CN112496336A (en) | 2020-11-13 | 2020-11-13 | Preparation method of gold nanocluster with multiple optical signal channels |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112496336A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101498719A (en) * | 2009-03-09 | 2009-08-05 | 东南大学 | Production method for enzyme functionalized nano immunity marker and use thereof |
| US20120238035A1 (en) * | 2011-03-18 | 2012-09-20 | Geddes Chris D | Multicolor microwave-accelerated metal-enhanced fluorescence (m-mamef) |
| US20150031571A1 (en) * | 2012-02-07 | 2015-01-29 | University Of Kansas | Chemiluminescent nanoparticles and uses thereof |
| CN104371705A (en) * | 2013-08-15 | 2015-02-25 | 中国科学技术大学 | Dual functionalized nanometer material, preparation method and uses thereof |
| CN105973874A (en) * | 2016-03-24 | 2016-09-28 | 中国农业科学院棉花研究所 | Detection method of 2,2-bis(4-hydroxyphenyl)propane in water |
| CN106984828A (en) * | 2017-03-28 | 2017-07-28 | 东南大学 | A kind of fluorescence gold nanoclusters fast synthesis method based on chemical etching |
| CN108500286A (en) * | 2017-09-28 | 2018-09-07 | 湖北医药学院 | A kind of preparation method of novel fluorescence gold nano cluster |
-
2020
- 2020-11-13 CN CN202011304908.3A patent/CN112496336A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101498719A (en) * | 2009-03-09 | 2009-08-05 | 东南大学 | Production method for enzyme functionalized nano immunity marker and use thereof |
| US20120238035A1 (en) * | 2011-03-18 | 2012-09-20 | Geddes Chris D | Multicolor microwave-accelerated metal-enhanced fluorescence (m-mamef) |
| US20150031571A1 (en) * | 2012-02-07 | 2015-01-29 | University Of Kansas | Chemiluminescent nanoparticles and uses thereof |
| CN104371705A (en) * | 2013-08-15 | 2015-02-25 | 中国科学技术大学 | Dual functionalized nanometer material, preparation method and uses thereof |
| CN105973874A (en) * | 2016-03-24 | 2016-09-28 | 中国农业科学院棉花研究所 | Detection method of 2,2-bis(4-hydroxyphenyl)propane in water |
| CN106984828A (en) * | 2017-03-28 | 2017-07-28 | 东南大学 | A kind of fluorescence gold nanoclusters fast synthesis method based on chemical etching |
| CN108500286A (en) * | 2017-09-28 | 2018-09-07 | 湖北医药学院 | A kind of preparation method of novel fluorescence gold nano cluster |
Non-Patent Citations (1)
| Title |
|---|
| JIAN SUN等: "11-Mercaptoundecanoic acid directed one-pot synthesis of water-soluble fluorescent gold nanoclusters and their use as probes for sensitive and selective detection of Cr3+ and Cr6+", 《JOURNAL OF MATERIALS CHEMISTRY C》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Recent advances in fluorescence probes based on carbon dots for sensing and speciation of heavy metals | |
| Hassanzadeh et al. | Specific fluorometric assay for direct determination of amikacin by molecularly imprinting polymer on high fluorescent g-C3N4 quantum dots | |
| Liu et al. | Recent progress on gold-nanocluster-based fluorescent probe for environmental analysis and biological sensing | |
| Huang et al. | Carbon quantum dots: synthesis, properties, and sensing applications as a potential clinical analytical method | |
| Patel et al. | Mn-doped ZnS quantum dots–an effective nanoscale sensor | |
| Zhong et al. | MoS 2 quantum dots as a unique fluorescent “turn-off–on” probe for the simple and rapid determination of adenosine triphosphate | |
| Tan et al. | Detection mechanism and the outlook of metal-organic frameworks for the detection of hazardous substances in milk | |
| Gupta et al. | PC12 live cell ultrasensitive neurotransmitter signaling using high quantum yield sulphur doped carbon dots and its extracellular Ca2+ ion dependence | |
| Sharma et al. | Surface decoration of ZnO nanoparticles: A new strategy to fine tune the recognition properties of imine linked receptor | |
| CN111141711A (en) | Nitrite detection method based on carbon nitride quantum dots | |
| Chen et al. | An eco-friendly near infrared fluorescence molecularly imprinted sensor based on zeolite imidazolate framework-8 for rapid determination of trace trypsin | |
| Ahmed et al. | Multifunctional dual emissive fluorescent probe based on europium-doped carbon dots (Eu-TCA/NCDs) for highly selective detection of chloramphenicol, Hg 2+ and Fe 3+ | |
| Chen et al. | " Light-on" Colorimetric Assay for Ascorbic Acid Detection via Boosting the Peroxidase-like Activity of Fe-MIL-88 | |
| Li et al. | Enzyme-induced biomineralization of cupric subcarbonate for ultrasensitive colorimetric immunosensing of carcinoembryonic antigen | |
| CN112461818B (en) | Gold nanocluster with multiple optical signal channels | |
| Sheng et al. | Selective detection of Cu2+ using nitrogen-doped carbon dots derived from humic acid and urea based on specific inner filter effect | |
| Wang et al. | A multifunctional upconversion nanoparticles probe for Cu2+ sensing and pattern recognition of biothiols | |
| Narayanan | Nanoparticles of different shapes for biosensor applications | |
| Rayappa et al. | Advances and effectiveness of metal–organic framework based bio/chemical sensors for rapid and ultrasensitive probing of antibiotic residues in foods | |
| Zhang et al. | Bimetal MOFs catalyzed Fenton-like reaction for dual-mode detection of thiamphenicol | |
| Zhang et al. | A fluorometric assay for α-glucosidase activity based on quaternary AgInZnS QDs | |
| Liu et al. | One-pot synthesis of strongly fluorescent DNA-CuInS2 quantum dots for label-free and ultrasensitive detection of anthrax lethal factor DNA | |
| CN112461819B (en) | Application of gold nanocluster with multiple optical signal channels | |
| CN108707644B (en) | Method for detecting pyrophosphate and alkaline phosphohydrolase based on DNA templated copper cluster probe | |
| Liu et al. | Fabrication of an activatable hybrid persistent luminescence nanoprobe for background-free bioimaging-guided investigation of food-borne aflatoxin in vivo |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20210316 |