CN113372902A - DNA composite gel for optical information storage and preparation method thereof - Google Patents
DNA composite gel for optical information storage and preparation method thereof Download PDFInfo
- Publication number
- CN113372902A CN113372902A CN202110633163.3A CN202110633163A CN113372902A CN 113372902 A CN113372902 A CN 113372902A CN 202110633163 A CN202110633163 A CN 202110633163A CN 113372902 A CN113372902 A CN 113372902A
- Authority
- CN
- China
- Prior art keywords
- rare earth
- preparation
- aqueous solution
- trichloride
- dna composite
- 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
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 230000003287 optical effect Effects 0.000 title abstract description 25
- 238000003860 storage Methods 0.000 title abstract description 23
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 70
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 54
- 239000007864 aqueous solution Substances 0.000 claims abstract description 34
- 239000000243 solution Substances 0.000 claims abstract description 33
- -1 terpyridine cation Chemical class 0.000 claims abstract description 32
- 108020004707 nucleic acids Proteins 0.000 claims abstract description 13
- 102000039446 nucleic acids Human genes 0.000 claims abstract description 13
- 150000007523 nucleic acids Chemical class 0.000 claims abstract description 13
- 239000002244 precipitate Substances 0.000 claims description 25
- 230000010355 oscillation Effects 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 11
- 238000004108 freeze drying Methods 0.000 claims description 9
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical group Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- BOXVSFHSLKQLNZ-UHFFFAOYSA-K dysprosium(iii) chloride Chemical compound Cl[Dy](Cl)Cl BOXVSFHSLKQLNZ-UHFFFAOYSA-K 0.000 claims description 4
- 230000008961 swelling Effects 0.000 claims description 4
- GFISHBQNVWAVFU-UHFFFAOYSA-K terbium(iii) chloride Chemical compound Cl[Tb](Cl)Cl GFISHBQNVWAVFU-UHFFFAOYSA-K 0.000 claims description 4
- 239000003880 polar aprotic solvent Substances 0.000 claims description 3
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 claims description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 2
- BHXBZLPMVFUQBQ-UHFFFAOYSA-K samarium(iii) chloride Chemical compound Cl[Sm](Cl)Cl BHXBZLPMVFUQBQ-UHFFFAOYSA-K 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims 2
- 238000003260 vortexing Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 24
- 238000000034 method Methods 0.000 abstract description 15
- 239000000758 substrate Substances 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 4
- 238000004020 luminiscence type Methods 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 abstract 1
- 108020004414 DNA Proteins 0.000 description 42
- 239000000499 gel Substances 0.000 description 21
- 239000007788 liquid Substances 0.000 description 20
- 238000002156 mixing Methods 0.000 description 18
- 238000003756 stirring Methods 0.000 description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 241000972773 Aulopiformes Species 0.000 description 7
- 235000019515 salmon Nutrition 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 5
- 238000007710 freezing Methods 0.000 description 5
- 230000008014 freezing Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000011232 storage material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000017 hydrogel Substances 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 description 2
- VFZRZRDOXPRTSC-UHFFFAOYSA-N 3,5-Dimethoxybenzaldehyde Chemical compound COC1=CC(OC)=CC(C=O)=C1 VFZRZRDOXPRTSC-UHFFFAOYSA-N 0.000 description 2
- 102000053602 DNA Human genes 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-O 1-methylimidazole Chemical compound CN1C=C[NH+]=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-O 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- AJKVQEKCUACUMD-UHFFFAOYSA-N 2-Acetylpyridine Chemical compound CC(=O)C1=CC=CC=N1 AJKVQEKCUACUMD-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical class [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H21/00—Compounds containing two or more mononucleotide units having separate phosphate or polyphosphate groups linked by saccharide radicals of nucleoside groups, e.g. nucleic acids
- C07H21/04—Compounds containing two or more mononucleotide units having separate phosphate or polyphosphate groups linked by saccharide radicals of nucleoside groups, e.g. nucleic acids with deoxyribosyl as saccharide radical
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
- G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
- G11B7/249—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing organometallic compounds
- G11B7/2492—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing organometallic compounds neutral compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Biotechnology (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Inorganic Chemistry (AREA)
- Saccharide Compounds (AREA)
- Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
Abstract
本发明涉及材料制备技术领域，尤其涉及一种用于光信息存储的DNA复合凝胶及其制备方法。该稀土DNA复合凝胶由核酸溶液、三联吡啶阳离子衍生物水溶液和稀土氯化物制成。实验表明，该稀土DNA复合凝胶可用于柔性基底的光信息存储，具有良好的可塑性、可加工性和高力学性能，可用于各种不同形态宏观材料的加工，以稀土DNA复合有机凝胶的荧光作为编码基元进行编码，可以完成信息的加密性写入和存储，且信息可以在柔性基底上进行有效存储，为稀土发光在信息柔性化应用开辟了道路。本发明制备方法工艺简单，可操作性高。The invention relates to the technical field of material preparation, in particular to a DNA composite gel for optical information storage and a preparation method thereof. The rare earth DNA composite gel is made of nucleic acid solution, terpyridine cation derivative aqueous solution and rare earth chloride. Experiments show that the rare earth DNA composite gel can be used for optical information storage on flexible substrates, with good plasticity, processability and high mechanical properties, and can be used for the processing of various macroscopic materials. Fluorescence is encoded as a coding primitive, which can complete the encrypted writing and storage of information, and the information can be effectively stored on flexible substrates, which opens up a way for the application of rare earth luminescence in information flexibility. The preparation method of the invention has simple process and high operability.
Description
Technical Field
The invention relates to the technical field of material preparation, in particular to a DNA composite gel for optical information storage and a preparation method thereof.
Background
With the explosive development of information technology, a large amount of invalid information fills our lives, and people pay more and more attention to the information protection work. The information coding and information storage are carried out by utilizing the light, so that the information safety can be effectively guaranteed, and the development prospect is wide. At present, the optical information storage material is mainly concentrated on a hard material substrate, and the flexible and processable optical information storage material needs to be further researched, so that the further development of the flexible optical information storage device is limited. Therefore, the search for macroscopic materials with flexibility and processability to achieve data encoding and decoding applications remains an urgent problem to be solved.
The rare earth material has unique optical characteristics and is widely applied to the aspects of information storage and anti-counterfeiting in recent years. Compared with luminescent materials such as organic micromolecules, perovskite, quantum dots and the like, the rare earth material has unique optical characteristics such as multiple excitation wavelengths, multicolor emission, long fluorescence life and the like, and the optical characteristics expand the application of the rare earth material in the fields of optical storage, encryption, anti-counterfeiting and the like. However, optical information storage using rare earths often relies on nanomaterials and an external carrier, and the information carried is usually fixed and difficult to re-edit and modify. Therefore, optimizing rare earth materials to produce a flexible and processable rare earth optical information storage material remains a challenge.
The fluorescent hydrogel and the multi-dimensional information storage system and method disclosed in publication number CN110903495A are prepared by mixing a fluorescent monomer with acrylamide, acrylic acid, an initiator and a cross-linking agent to prepare a pre-polymerization solution, and performing a polymerization reaction on the pre-polymerization solution to prepare the fluorescent hydrogel capable of storing information. Patterned storage of information is achieved by forming a printed pattern on the fluorescent hydrogel using a dye printing agent. However, the method has complicated operation steps, and the influence of the flexibility and deformation effect of the material on information is not involved, so that the application and the expansion of the gel material on a flexible substrate are limited to a certain extent.
Disclosure of Invention
In order to overcome the problems that optical information storage materials in the prior art are low in flexibility and processability, are limited in application in the using process and low in mechanical strength of the conventional rare earth organogel materials, the invention provides the rare earth DNA composite organogel for optical information storage and the preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of rare earth DNA composite gel, which comprises the following steps:
mixing the nucleic acid solution, the terpyridine cation derivative aqueous solution and the rare earth chloride aqueous solution, and immediately performing vortex oscillation to obtain a mixed solution;
and centrifuging and freeze-drying the mixed solution, and adding an organic solvent for swelling to obtain the rare earth DNA composite organogel.
The DNA composite gel prepared from the nucleic acid solution, the terpyridine cation derivative aqueous solution and the rare earth chloride can be used for optical information storage of a flexible substrate, and has good plasticity, processability and high mechanical property.
The rare earth material has unique optical characteristics, such as multiple excitation wavelengths, multicolor emission, long fluorescence life and the like, and is widely applied to the fields of optical storage, encryption, anti-counterfeiting and the like. The rare earth material is combined with the stretchable flexible material, so that the fluorescence characteristic of the original rare earth material can be maintained, and meanwhile, the stretchable flexible material is endowed with the characteristic of flexibility and processability and can be used for further information encoding.
The DNA macromolecule chain has stable complementary pairing base, the mutual stacking interaction between the bases enhances the strength of the DNA molecule chain, and in addition, the large number of phosphoric acid functional groups also provides sites for reaction with other substances, so that the material is an ideal choice for preparing the stretchable flexible material.
According to the invention, DNA macromolecules are matched with the terpyridine cation derivatives by further utilizing the coulomb effect, so that the interaction between DNA molecular chains is improved. In addition, the interaction of the whole complex network system is further enhanced by introducing rare earth elements and terpyridine cation derivatives for coordination, and the fluorescence characteristic of rare earth is introduced into the whole complex system, so that the rare earth DNA composite organogel with high mechanical strength is prepared.
In some embodiments, the volume ratio of the nucleic acid solution, the terpyridine cation derivative aqueous solution, and the rare earth chloride aqueous solution is 1: (0.01-0.15). In some embodiments, the ratio may be 1:1:0.05, 1:1:0.12, 1:1: 0.1.
In some embodiments, the concentration of the nucleic acid solution is 2-20 mg/ml, and in some embodiments may be 10mg/ml or 15 mg/ml.
In the present invention, the nucleic acid solution is an aqueous nucleic acid solution. Wherein, the nucleic acid is preferably double-stranded DNA, the molecular weight is preferably 10-1000 ten thousand Da, and the nucleic acid can be obtained in the market or extracted by a conventional method. In a specific embodiment of the invention, the nucleic acid is salmon sperm DNA, which is commercially available.
In some embodiments, the concentration of the terpyridine cation derivative aqueous solution is 2-20 mg/ml, and in some embodiments, the concentration may be 10mg/ml or 15 mg/ml. Wherein, the terpyridine dication derivative is a long chain section with one end provided with a terpyridine group and the other end provided with dication; in some embodiments, the terpyridine cation derivative is 1,1' - (((5- ([2,2':6', 2' -terpyridine ] -4' -yl) -1, 3-phenylene) bis (oxy)) bis (hexane-6, 1-diyl)) bis (3-methyl-1H-imidazol-3-ium), which has the structure shown in FIG. 1 and is synthesized by the following steps:
3, 5-dimethoxybenzaldehyde (3.32g,20mmol) and 2-acetylpyridine (4.84g,40mmol) were put into a 250mL flask and dissolved with 100mL of absolute ethanol under stirring. Ground KOH (3.08g, 35mmol) was added and the reaction was carried out at room temperature for 12 hours. 60mL of 25% aqueous ammonia was added to the mixture, and the mixture was heated to 60 ℃ to react for 24 hours. And (4) carrying out suction filtration, washing a filter cake by using absolute ethyl alcohol, drying and carrying out silica gel column chromatography to obtain an intermediate 1.
Intermediate 1(3.69g,10mmol) was dissolved in 80mL hydrobromic acid (40%), oil at 130 ℃ overnight, HBr was removed by rotary evaporation, the resulting yellow solid was washed with saturated sodium bicarbonate, the precipitate turned purple, filtered with suction, and dried to give intermediate 2.
1, 6-dibromohexane (12.1g,50mmol) and 2g potassium carbonate were dissolved in 100mL acetonitrile and heated to 70 ℃. Intermediate 2(1.7g,5mmol) was dissolved in 20mL acetonitrile and slowly added dropwise to the flask and reacted for 24 h. After the reaction was completed, the mixture was filtered. The filtrate is evaporated by rotation, and the intermediate 3 is obtained by silica gel column chromatography.
1 methylimidazole (0.82g,10mmol) and intermediate 3(1g,1.5mmol) were dissolved in 100mL acetonitrile and refluxed at 80 ℃ for 24 hours. Cooling to room temperature, rotary evaporating, dissolving with small amount of water, and precipitating with large amount of ethyl acetate. The resulting crystals were dissolved in water and lyophilized to give compound 4, the final product.
In some embodiments, the concentration of the aqueous rare earth chloride solution is 0.005 to 0.015 mol/ml. In some embodiments, red, the concentration of the aqueous rare earth chloride solution is 0.01 mol/ml.
Wherein the rare earth chloride is at least one of europium trichloride, terbium trichloride, lanthanum trichloride, cerium trichloride, dysprosium trichloride and samarium trichloride. In some embodiments, the rare earth chloride is specifically dysprosium trichloride, europium trichloride, or a mixture of europium trichloride and terbium trichloride.
In the invention, the frequency of vortex oscillation is 1800-3200 r/min, and the time is 2-10 min.
In some embodiments, the centrifugation is at 8000 to 12000rpm for 2 to 5 min; in some embodiments, the centrifugation is at 10000rpm for 2 min.
In the preparation method provided by the invention, the steps of washing the precipitate with water and adding water for vortex oscillation are also included after the centrifugation and before the freeze-drying; the number of times of washing and precipitating is 2-4, the frequency of vortex oscillation is 1800-3200 r/min, and the time is 2-10 min. In some embodiments, the number of washing the precipitate with water is 3, the frequency of vortex oscillation is 2500r/min, and the time is 2 min.
In the present invention, the organic solvent is a polar aprotic solvent; the polar aprotic solvent is one or more of dimethyl sulfoxide, N-dimethylformamide or N-methylpyrrolidone; the swelling time is 24-72 h.
In some embodiments, the preparation method specifically comprises the following steps:
the method comprises the following steps: preparing a salmon sperm DNA aqueous solution with the mass fraction of 2-20 mg/ml, and fully shaking and stirring uniformly;
step two: preparing a terpyridine cation derivative aqueous solution with the mass fraction of 2-20 mg/ml, and fully shaking and stirring uniformly;
step three: preparing 0.01mol/ml rare earth trichloride aqueous solution, fully shaking and stirring uniformly;
step four: and (3) respectively taking 1ml of the solution obtained in the first step and the solution obtained in the second step, mixing the solution with the same volume, and simultaneously adding 10-150 mu L of the liquid prepared in the third step. Mixing the above liquids, and immediately performing vortex oscillation for 2 min;
step five: centrifuging the mixed liquid in the fourth step for 2min at 10000rpm, adding 1ml of distilled water into the centrifuged precipitate, and performing vortex oscillation for 2 min;
step six: repeating the step five twice, and fully washing the precipitate obtained in the step five with water;
step seven: putting the precipitate obtained in the sixth step into liquid nitrogen for freezing, and simultaneously putting the precipitate into a freeze dryer for freeze-drying treatment;
step eight: and (3) placing the freeze-dried product obtained in the step seven into a dimethyl sulfoxide solution to be soaked (i.e. swelled) for 12-72 h, and uniformly mixing after soaking to obtain the rare earth DNA composite organic gel for optical information storage.
The invention also provides the rare earth DNA composite gel prepared by the preparation method.
According to the invention, by reasonably controlling the doped rare earth elements and the content of the rare earth elements, the fluorescence characteristic of the prepared rare earth DNA composite organogel can be regulated and controlled, so that the rare earth DNA composite organogel can emit fluorescence with a specific wavelength under 405nm ultraviolet light. The rare earth DNA composite organogel has fluorescence characteristic and plasticity, can be used for processing various macroscopic materials with different forms, can effectively store information on a flexible substrate due to the plasticity and the processability of the material, and opens up a way for the application of rare earth luminescence in information flexibility. In addition, the fluorescence of the rare earth DNA composite organic gel is used as a coding element for coding, and the information can be written and stored in an encrypted manner. Meanwhile, the method has the advantages of simple process, convenient preparation and high operability.
Drawings
FIG. 1 is a chemical structure diagram of a terpyridine cation derivative of the present invention;
FIG. 2 shows the tensile mechanical properties of the organogel prepared in example 1;
FIG. 3 is a rare earth organogel fluorescent two-dimensional code pattern prepared in example 2;
FIG. 4 is a fluorescent encoding pattern of rare earth organogel prepared in example 3;
FIG. 5 is a fluorescent encoding pattern of rare earth organogel after stretching prepared in example 3;
FIG. 6 is a fluorescent encoding pattern of the rare earth organogel after bending prepared by example 3.
Detailed Description
The invention provides a rare earth DNA composite gel and a preparation method thereof. Those skilled in the art can modify the process parameters appropriately to achieve the desired results with reference to the disclosure herein. It is expressly intended that all such similar substitutes and modifications which would be obvious to one skilled in the art are deemed to be included in the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.
The test materials adopted by the invention are all common commercial products and can be purchased in the market.
The invention provides a preparation method of rare earth DNA composite gel, which comprises the following steps:
mixing a salmon sperm DNA aqueous solution, a terpyridine cation derivative aqueous solution and a rare earth chloride aqueous solution, and immediately performing vortex oscillation to obtain a mixed solution;
and centrifuging and freeze-drying the mixed solution, and adding an organic solvent for swelling to obtain the rare earth DNA composite organogel.
In some embodiments, the preparation method specifically comprises the steps of:
the method comprises the following steps: preparing a salmon sperm DNA aqueous solution with the mass fraction of 2-20 mg/ml, and fully shaking and stirring uniformly;
step two: preparing a terpyridine cation derivative aqueous solution with the mass fraction of 2-20 mg/ml, and fully shaking and stirring uniformly;
step three: preparing 0.01mol/ml rare earth trichloride aqueous solution, fully shaking and stirring uniformly;
step four: and (3) respectively taking 1ml of the solution obtained in the first step and the solution obtained in the second step, mixing the solution with the same volume, and simultaneously adding 10-150 mu L of the liquid prepared in the third step. Mixing the above liquids, and immediately performing vortex oscillation for 2 min;
step five: centrifuging the mixed liquid in the fourth step for 2min at 10000rpm, adding 1ml of distilled water into the centrifuged precipitate, and performing vortex oscillation for 2 min;
step six: repeating the step five twice, and fully washing the precipitate obtained in the step five with water;
step seven: putting the precipitate obtained in the sixth step into liquid nitrogen for freezing, and simultaneously putting the precipitate into a freeze dryer for freeze-drying treatment;
step eight: and (3) placing the freeze-dried product obtained in the step seven into a dimethyl sulfoxide solution to be soaked (i.e. swelled) for 12-72 h, and uniformly mixing after soaking to obtain the rare earth DNA composite organic gel for optical information storage.
The invention is further illustrated by the following examples:
example 1:
a preparation method of rare earth DNA composite organic gel for optical information storage comprises the following steps:
the method comprises the following steps: preparing salmon sperm DNA aqueous solution with the mass fraction of 15mg/ml, and fully shaking and stirring uniformly;
step two: preparing a terpyridine cation derivative aqueous solution with the mass fraction of 15mg/ml, and fully shaking and stirring uniformly;
step three: preparing a 0.01mol/ml dysprosium trichloride aqueous solution, fully shaking and stirring uniformly;
step four: and (3) respectively taking 1ml of the solution obtained in the first step and the solution obtained in the second step, mixing the solutions in equal volumes, and simultaneously adding 50 mu L of the liquid prepared in the third step. Mixing the above liquids, and immediately performing vortex oscillation for 2 min;
step five: centrifuging the mixed liquid in the fourth step for 2min at 10000rpm, adding 1ml of distilled water into the centrifuged precipitate, and performing vortex oscillation at 2500rpm for 3 min;
step six: repeating the fifth step twice, and fully washing the precipitate obtained in the fourth step with water;
step seven: putting the precipitate obtained in the sixth step into liquid nitrogen for freezing, and simultaneously putting the precipitate into a freeze dryer for freeze-drying treatment;
step eight: and (5) placing the freeze-dried product obtained in the step seven into a dimethyl sulfoxide solution to be soaked for 72 hours, and uniformly mixing after soaking.
Step nine: and (3) detecting the mechanical property of the rare earth DNA composite organic gel. The prepared organogel is stretched and then collected by a yarn collecting strand, and the collected organogel yarn is subjected to mechanical property test, which is shown in fig. 2. The result shows that the prepared rare earth DNA composite organogel has strong mechanical property.
Example 2:
a preparation method of rare earth DNA composite organic gel for optical information storage comprises the following steps:
the method comprises the following steps: preparing salmon sperm DNA aqueous solution with the mass fraction of 15mg/ml, and fully shaking and stirring uniformly;
step two: preparing a terpyridine cation derivative aqueous solution with the mass fraction of 15mg/ml, and fully shaking and stirring uniformly;
step three: preparing 0.01mol/ml europium trichloride aqueous solution, fully shaking and stirring uniformly;
step four: and (3) respectively taking 1ml of the solution obtained in the first step and the solution obtained in the second step, mixing the solutions in equal volumes, and simultaneously adding 120 mu L of the liquid prepared in the third step. Mixing the above liquids, and immediately performing vortex oscillation for 2 min;
step five: centrifuging the mixed liquid in the fourth step for 2min at 10000rpm, adding 1ml of distilled water into the centrifuged precipitate, and performing vortex oscillation at 1800rpm for 5 min;
step six: repeating the fifth step twice, and fully washing the precipitate obtained in the fourth step with water;
step seven: putting the precipitate obtained in the sixth step into liquid nitrogen for freezing, and simultaneously putting the precipitate into a freeze dryer for freeze-drying treatment;
step eight: and (5) placing the freeze-dried product obtained in the step seven into a dimethyl sulfoxide solution to be soaked for 72 hours, and uniformly mixing after soaking.
Step nine: and (3) carrying out fluorescence coding test on the rare earth DNA composite organic gel. And editing the shape of the rare earth DNA organogel through a die to prepare a rare earth organogel two-dimensional code pattern with a certain shape. The prepared gel emits red fluorescence under the irradiation of 405nm ultraviolet light, and meanwhile, the stored information can be collected through mobile phone scanning, as shown in fig. 3.
Example 3:
a preparation method of rare earth DNA composite organic gel for optical information storage comprises the following steps:
the method comprises the following steps: preparing salmon sperm DNA aqueous solution with the mass fraction of 10mg/ml, and fully shaking and stirring uniformly;
step two: preparing a terpyridine cation derivative aqueous solution with the mass fraction of 10mg/ml, and fully shaking and stirring uniformly;
step three: respectively preparing 0.01mol/ml europium trichloride and terbium trichloride aqueous solutions, and fully shaking and stirring the aqueous solutions uniformly;
step four: and (3) respectively taking 1ml of the solution obtained in the first step and the solution obtained in the second step, mixing the solutions in equal volumes, and simultaneously adding 100 mu L of the liquid prepared in the third step. Mixing the above liquids, and immediately performing vortex oscillation for 2 min;
step five: centrifuging the mixed liquid in the fourth step for 2min at 10000rpm, adding 1ml of distilled water into the centrifuged precipitate, and performing vortex oscillation at 3200rpm for 2 min;
step six: repeating the fifth step twice, and fully washing the precipitate obtained in the fourth step with water;
step seven: putting the precipitate obtained in the sixth step into liquid nitrogen for freezing, and simultaneously putting the precipitate into a freeze dryer for freeze-drying treatment;
step eight: and (5) placing the freeze-dried product obtained in the step seven into a dimethyl sulfoxide solution to be soaked for 72 hours, and uniformly mixing after soaking.
Step nine: and carrying out fluorescence coding on the rare earth DNA composite organic gel and testing the plasticity and the information retention of the organic gel on the soft bottom material. Respectively cutting the europium-doped rare earth DNA organogel and the terbium-doped rare earth DNA organogel into organogel strips with relatively consistent sizes. The europium-doped rare earth DNA organogel emits red fluorescence under the irradiation of 405nm ultraviolet light, and the terbium-doped rare earth DNA organogel emits green fluorescence under the irradiation of 405nm ultraviolet light. And (3) carrying out information coding by taking the emitted fluorescent color as a storage unit, wherein the red is marked as '0' and the green is marked as '1'. The rare earth organogel was placed on a stretchable soft substrate and data "19" was encoded into the rare earth organogel. When the ultraviolet light is not irradiated, no information can be read, and the stored '19' information can be read under the irradiation of the ultraviolet light with the wavelength of 405nm, as shown in figure 4. In addition, the rare earth DNA composite gel is also deformed when the soft substrate is stretched and bent, but the stored information is not changed, as shown in FIGS. 5 and 6, respectively, the prepared rare earth organic gel can be used for optical information storage of the flexible substrate.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that it is obvious to those skilled in the art that various modifications and improvements can be made without departing from the principle of the present invention, and these modifications and improvements should also be considered as the protection scope of the present invention.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110633163.3A CN113372902B (en) | 2021-06-07 | 2021-06-07 | DNA composite gel for optical information storage and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110633163.3A CN113372902B (en) | 2021-06-07 | 2021-06-07 | DNA composite gel for optical information storage and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113372902A true CN113372902A (en) | 2021-09-10 |
| CN113372902B CN113372902B (en) | 2022-10-14 |
Family
ID=77576310
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110633163.3A Active CN113372902B (en) | 2021-06-07 | 2021-06-07 | DNA composite gel for optical information storage and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113372902B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114708886A (en) * | 2022-04-25 | 2022-07-05 | 南京邮电大学 | Thermosensitive erasable plasma excimer nano biological memory and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105838711A (en) * | 2016-05-09 | 2016-08-10 | 张阳 | Single-stranded deoxyribonucleic acid for information storage and encryption |
| CN109913977A (en) * | 2019-03-15 | 2019-06-21 | 中国科学院长春应用化学研究所 | A kind of nucleic acid gel fiber and preparation method thereof |
| CN110903495A (en) * | 2018-09-14 | 2020-03-24 | 中国科学院宁波材料技术与工程研究所 | Fluorescent hydrogel, multi-dimensional information storage system and method |
| CN111888324A (en) * | 2020-06-29 | 2020-11-06 | 中国科学院长春应用化学研究所 | An injectable rare earth-DNA photohydrogel, its preparation method and application |
-
2021
- 2021-06-07 CN CN202110633163.3A patent/CN113372902B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105838711A (en) * | 2016-05-09 | 2016-08-10 | 张阳 | Single-stranded deoxyribonucleic acid for information storage and encryption |
| CN110903495A (en) * | 2018-09-14 | 2020-03-24 | 中国科学院宁波材料技术与工程研究所 | Fluorescent hydrogel, multi-dimensional information storage system and method |
| CN109913977A (en) * | 2019-03-15 | 2019-06-21 | 中国科学院长春应用化学研究所 | A kind of nucleic acid gel fiber and preparation method thereof |
| CN111888324A (en) * | 2020-06-29 | 2020-11-06 | 中国科学院长春应用化学研究所 | An injectable rare earth-DNA photohydrogel, its preparation method and application |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114708886A (en) * | 2022-04-25 | 2022-07-05 | 南京邮电大学 | Thermosensitive erasable plasma excimer nano biological memory and preparation method thereof |
| CN114708886B (en) * | 2022-04-25 | 2024-01-19 | 南京邮电大学 | A thermally sensitive and rewritable plasmon nanobiomemory and its preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113372902B (en) | 2022-10-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Nie et al. | Multiaddressable photochromic architectures: from molecules to materials | |
| Nidhankar et al. | Efficient metal-free organic room temperature phosphors | |
| Huang et al. | Tailoring tunable luminescence via supramolecular assembly strategies | |
| Zhao et al. | Dual-mode induction of tunable circularly polarized luminescence from chiral metal-organic frameworks | |
| Xu et al. | Excited state modulation for organic afterglow: materials and applications | |
| Sánchez-Ruiz et al. | Aggregation-induced emission properties in fully π-conjugated polymers, dendrimers, and oligomers | |
| Hu et al. | Multicolor circularly polarized luminescence of a single-component system revealing multiple information encryption | |
| Yin et al. | Supramolecular chirality induced by chiral solvation in achiral cyclic Azo-containing polymers: topological effects on chiral aggregation | |
| Hu et al. | Aggregation-induced-emission-active vinamidinium salts with tunable emissions, reversible mechanochromic response and the application in data-security protection | |
| Zhao et al. | Hydrolyzation-triggered ultralong room-temperature phosphorescence in biobased nonconjugated polymers | |
| Ma et al. | A new strategy to fabricate multifunctional luminescent MOFs, extending their application range from pH sensing to amino acid information coding | |
| CN113372902A (en) | DNA composite gel for optical information storage and preparation method thereof | |
| Wang et al. | Pyrene-based metallocycles and metallocages: more than fluorophores | |
| Ma et al. | Macrocycle γ-cyclodextrin confined polymeric chromophore ultralong phosphorescence energy transfer | |
| Wang et al. | Multiple stimulus responsive Co-AIE framework materials with reversible solvatochromic and thermochromic behaviors: molecular design, synthesis and characterization | |
| Chan et al. | Chiral Poly (4‐ethynylbenzoyl‐L‐valine)‐Induced Helical Self‐Assembly of Alkynylplatinum (II) Terpyridyl Complexes with Tunable Electronic Absorption, Emission, and Circular Dichroism Changes | |
| Zhang et al. | Tetraphenylethene-based macrocycles with dual-ring topology: synthesis, structures, and applications | |
| Chen et al. | Asymmetric diarylamine guests for a host–guest system with stimulus-responsive room temperature phosphorescence | |
| CN103881073A (en) | Preparation method of fluorescent polymer capable of realizing fluorescence enhancement by using self-assembly | |
| CN108822074B (en) | A kind of dithiophene vinyl compound with tetrastyrene unit and preparation method and application thereof | |
| CN111607102B (en) | Covalent organic framework material, preparation method and application thereof | |
| Zhou et al. | 3D printed hydrogels with time/temperature-dependent photoluminescence for multi-information dynamic display | |
| Huang et al. | Initialing Circularly Polarized Room-Temperature Phosphorescence from Purely Organic Luminophore Aggregate | |
| Fu et al. | Visible–light–modulating cucurbit [8] uril–mediated reversibly tunable Multicolor–Light emission | |
| Lin et al. | From elementary to advanced: rational design of single component phosphorescence organogels for anti-counterfeiting applications |
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 |