CN114621747B - Europium-natural glycan doped living diatom efficient luminescent material and preparation method thereof - Google Patents
Europium-natural glycan doped living diatom efficient luminescent material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a europium-natural glycan doped living diatom efficient luminescent material and a preparation method thereof. Europium-natural polysaccharide is added into the well-grown algae cell culture solution for a small amount for many times, so that the damage to the activity of diatom is reduced as much as possible. Living diatoms propagate in a cell division manner, and parent diatoms are deposited on vesicles after extracting nutrients from the medium, and then split into two child diatoms. The cell wall of the child diatom consists of the watchcase consisting of protoplasm from the parent diatom and the watchcase consisting of material from the medium. At least two cell cycles are required to integrate europium-native glycans into both shell surfaces of the siliceous shell of living diatoms. In addition, the living diatom is used as a natural biological porous material, europium-natural polysaccharide can be encapsulated in the diatom pore canal, and the fluorescence characteristic can be further enhanced.
Description
Technical Field
The invention relates to a high-efficiency luminous biological material obtained based on europium-natural polysaccharide doped living diatom and a preparation method thereof.
Background
Algae use solar energy to carry out photosynthesis, and are organisms with the highest success in light energy utilization and highest light energy utilization rate in the world. Diatom is mostly propagated in a cell division mode, is easy to culture and convenient to control the purity of algae cells, is mostly composed of amorphous silicon dioxide, and also contains organic components of polyamine and silicon wax protein. Recently, it has been examined that even mycosporine-like amino acids exhibit UV absorption between 320nm and 340nm, protecting cells from UV radiation. The biggest secret of the algae for efficiently utilizing sunlight is the shell, and the diatom shell is a nano-scale screen-shaped structure composed of silicon dioxide with extremely complex and precise structure. The unique natural porous nano structure and photonic crystal characteristics lead diatom to attract attention of a plurality of researchers in the fields of photonics, fluorescence sensing, ultraviolet protection and the like.
Lanthanide complexes synthesized from lanthanoids are a research hotspot due to their efficient luminescence properties. Among these ions formed of lanthanoid elements, eu 3+ Ions can produce high photoluminescence, high quantum yields due to their rich energy levels and the special properties of the 4f electron transitions. In recent years, the group of subjects has also been devoted to the study of lanthanide complexes, which have found great potential in the protection of lanthanoids from ultraviolet light. It was found that the energy in the europium complex can be determined by the first ligand: triplet excited states (T) of 1, 10-Phenanthroline (PHEN), 4, 7-diphenyl-1, 10-phenanthroline (BATH), 2-Bipyridine (BIPY) and triphenylphosphine oxide (TPO) 1 ) To a second ligand: t of acetylacetone (ACAC), dibenzoylmethane (DBM), methylbenzotriazole (TTA) and Benzoylacetone (BA) 1 In the state of Eu 3+ Of ions 5 D 0 Excitation energy level transfer. The europium complex is excited by these energy level transitions to emit red light and absorb part of the ultraviolet light in the range of 200-400 nm. Lanthanide complexes are attractive materials for research in the field of uv protection.
Disclosure of Invention
The invention provides a preparation method for obtaining a high-efficiency luminescent material based on doped living diatom of europium-natural polysaccharide by utilizing a biological self-siliconizing process of living diatom cell division. When diatom cells are grown and split, europium-natural polysaccharide is added, and the complex polysaccharide aggregate is beneficial to the formation of diatom cell walls because the polysaccharide has good biocompatibility, so that europium-natural polysaccharide is used as a key component for absorbing and converting ultraviolet light to be fused into living diatom, and a biological hybrid similar to Mummy is prepared. Compared with diatom, the novel material greatly enhances ultraviolet absorption and has excellent luminous performance.
The invention adopts the following technical scheme:
a preparation method of a europium-natural glycan doped living diatom efficient luminescent material comprises the following steps:
(1) Doping of luminescent living diatom: when the algae cells stably grow, europium-natural polysaccharide is added according to the principle of a small number of times: selectingUnder the condition of illumination of the incubator, the method is to be carried out according to the algae species: medium = 1: (1-5) live diatom cultured in volume ratio were taken out from a cold light source incubator and put into an ultra clean bench, and 1X 10 per 50ml of algal seeds were added dropwise -4 moL/L-1×10 -3 moL/L europium-natural polysaccharide 50 muL-200 muL, adding dropwise while shaking, adjusting pH to 6.5-8.5 with acid and alkali, adding europium-natural polysaccharide dropwise once every 6-10 hours, shaking culture flask regularly, and shaking at 15-30deg.C for (12-24) h: (12-0) h of light and shade cycle cultivation of living diatom, illumination: 2000Lx-3000Lx;
(2) Obtaining a europium-natural polysaccharide doped living diatom efficient luminescent material: and (3) repeating the step (1) for 3-25 days, and then, obtaining the hybridized luminous living diatom after the living diatom suspension is treated.
According to the preparation method, after europium-natural polysaccharide is added into a culture medium, algae cells are split into upper and lower shells similar to a culture dish by utilizing the biological autosilicification principle of living diatom division, the other half of shells are reformed, and europium-natural polysaccharide participates in the formation of the cell walls of the algae cells, so that the high-efficiency luminescent material is prepared.
The preparation method comprises selecting living diatom as one of Haematococcus wilsonii, mei Nixiao Cycloalgae, phaeodactylum tricornutum, nicotiana microcephala and Phaeodactylum longum.
The preparation method prepares europium ions, ligands and polysaccharide of europium-natural polysaccharide with the concentration of respectively: euCl 3 Solution concentration 1X 10 -4 mol/L-5×10 -3 mol/L; concentration of ligand acetylacetone (ACAC), dibenzoylmethane (DBM), tolyltriazole (TTA) and Benzoylacetone (BA) solutions 3X 10 -4 mol/L-1.5×10 -2 mol/L; 1X 10 concentration of 1, 10-Phenanthroline (PHEN), 4, 7-diphenyl-1, 10-phenanthroline (BATH), 2-Bipyridine (BIPY) and triphenylphosphine oxide (TPO) solutions -4 mol/L-5×10 -3 mol/L; sodium hyaluronate (Na-Hya) solution was 1mg/mL and chitosan (Cs) solution was 1mg/mL.
The preparation method prepares EuCl as the ratio of the amounts of substances of europium-natural polysaccharide 3 ACAC: PHEN: na-Hya: cs=1:3:1:1:2; or EuCl 3 :DBM:BATH：Na-Hya：Cs＝1:3:1:1:2；EuCl 3 TTA: PHEN: na-Hya: cs=1:3:1:1:2; or EuCl 3 :BA:BIPY：Na-Hya：Cs＝1:3:1:1:2。
The preparation method comprises the following steps of: washing with physiological saline to remove impurities; then, one or more fixed water samples in various mixed solutions prepared from glutaraldehyde, low-concentration alcohol, glycerol and the medicaments according to the proportion are selected; after fixed standing, washing residual europium-natural polysaccharide with 15% -50% alcohol; the sample was frozen in an ultra-low temperature refrigerator at-80℃and the quenched frozen sample was freeze-dried.
The hybrid luminescent material based on the europium-natural polysaccharide doped by the living diatom prepared by any one of the methods, wherein the silicon hydroxyl groups existing in the living diatom and the hydroxyl groups of the europium-natural polysaccharide are combined by means of covalent bonds and hydrogen bonds.
Compared with the prior researches, the method disclosed by the invention has the advantages that the diatom framework is used as the raw material, the complex chemical process is saved, and the prepared diatom hybrid material has both organic and inorganic components, and is converted from a bone structure to a cortical structure. And simultaneously has good ultraviolet absorption and fluorescence performance.
The novel material has organic matters and amorphous silicon dioxide of diatom parts, and is doped with europium complex, thereby having advantages in the aspects of absorbing and converting ultraviolet light. Ultraviolet light can be converted to visible light for protection of the device.
Europium-natural polysaccharide is added into the well-grown algae cell culture solution for a small amount for many times, so that the damage to the activity of diatom is reduced as much as possible. Living diatoms propagate in a cell division manner, and parent diatoms are deposited on vesicles after extracting nutrients from the medium, and then split into two child diatoms. The cell wall of the child diatom consists of the watchcase consisting of protoplasm from the parent diatom and the watchcase consisting of material from the medium. At least two cell cycles are required to integrate europium-native glycans into both shell surfaces of the siliceous shell of living diatoms.
The invention uses living diatom with abundant raw materials and environmental protection as a carrier, and silicon hydroxyl groups existing in the diatom are combined with hydroxyl groups of europium-natural polysaccharide in a covalent bond and hydrogen bond mode, so that the luminescent material containing rare earth europium components is prepared. In contrast to synthetic silica materials, diatom porous materials can achieve extremely regular nanostructures in both the micrometer and sub-micrometer ranges, and in some cases cannot be replicated even manually. On the other hand, compared with the process of doping europium complex with diatom shells, the process adopts the hybrid material prepared by doping europium-natural polysaccharide with living diatom, so that the integrity of the diatom structure is ensured. And the experimental process is simplified, and the purposes of saving cost and protecting environment are achieved.
Drawings
FIG. 1 is an SEM image of a diatom of example 1 incorporating europium-natural polysaccharide;
FIG. 2 is a fluorescence microscope image of diatom algae doped with europium-natural polysaccharide in example 1;
FIG. 3 is an XPS spectrum of diatom added europium-natural polysaccharide in example 1;
FIG. 4 is a graph showing the ultraviolet absorption spectrum of europium-natural polysaccharide added to diatom algae in example 1;
fig. 5 shows (a) excitation spectra and (b) emission spectra of the diatom and europium-natural polysaccharide hybrid luminescent material of example 1.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1
(1) Using F/2 medium, according to Hai-chain seaweed Wei: medium = 1:3 (50 ml:150 ml) live diatoms were grown at a ratio of 12: the living diatoms were cultured with a 12-h light and dark cycle (light: 2000 Lx). Europium-natural polysaccharide is added into diatom culture solution with good growth condition, and 100 mu L of 1×10 is added -3 The standard of moL/L is that europium-natural polysaccharide is added successively, and the europium-natural polysaccharide is added once in the morning and at night. Eu (TTA) is added by adopting the principle of a small amount of a plurality of times in the biological siliconizing process of diatom 3 phen- (Na-Hya) -Cs were cultured for 20 days.
Preparation of europium-natural polysaccharide: 1mL of 1X 10 -3 EuCl of M 3 Solution and 1mL of 3X 10 -3 The TTA solution of M was stirred at 800rpm for 30min and then1mL of 1X 10 was added -3 Phen of M is reacted for 1h, then 1mL of Na-Hya is added dropwise and stirred for 1-2h, and finally 2mL of Cs is added dropwise and stirred for 1-2 h.
(2) Centrifuging the diatom suspension at 3000rpm, washing with normal saline, centrifuging for 3 times, and removing impurities; fixing the centrifuged sample with 2.5% glutaraldehyde solution, adding 5% of the sample volume according to the sample concentration, and standing at 4deg.C for 24 hr; then the fixed water sample is washed with 15% alcohol concentration, oscillated, centrifuged to remove supernatant, and the operation is repeated 3 times.
In fig. 1, after europium-natural polysaccharide is doped into living diatom, the morphology of diatom is not changed significantly, and fig. 1b and 1c show the characteristic structures of single diatom, respectively. It is clear that the living diatom is shaped like a short cylinder, resembling a disk. The shell surface is circular, the shell surface is radial, the shell surface is provided with a ring formed by a central supporting protrusion, a plurality of supporting protrusions are also arranged around the edge of the shell surface, and the surface is provided with pore decorations. The diameter of the seaweed is 7-11um, and the height is 4-8 um. The image under the fluorescence microscope of fig. 2 was observed and fluorescence of the sample was recorded using a fluorescence microscope equipped with objective lenses of 10 times (a), 20 times (b) and 40 times (c). As can be seen from the figure, the fluorescent hybrid sample is based on the appearance of diatoms, and takes on a disk shape. From fig. 2b and 2c, it can be seen that the europium complex successfully binds to diatom algae, demonstrating that the hybridized sample has significant luminescence properties. FIG. 3 is an XPS diagram of europium-natural polysaccharide and diatom hybridization luminescent material, the existence of europium, fluorine and other elements can be seen from the full spectrum diagram of FIG. 3a, the fine spectrum diagrams of FIG. 3b and FIG. 3C are compared, a new peak Si-O-C appears at 533.15ev, the combination of the silicon hydroxyl group existing in diatom and the hydroxyl group of europium-natural polysaccharide through covalent bond and hydrogen bond is proved, and the successful doping of europium-natural polysaccharide into living diatom is proved. In comparison with living diatom doped with europium-natural polysaccharide, as shown in FIG. 4, there is an absorption band at 258nm and 342nm, the absorption peak at 258nm is attributed to Phen ligand effect, and the absorption peak at 342nm is attributed to TTA ligand effect. The europium-natural polysaccharide was successfully doped with living diatom. The "diatom mumab" hybrid luminescent material shown in fig. 5 has (a) excitation spectrum and (b) emission spectrum, and it can be seen from the figure that the emission peak at 612nm is excited when the excitation light is 348nm, and has excellent fluorescence characteristics.
Example 2
(1) Using Csi medium, according to Mei Nixiao, the following seaweeds: medium = 1:2 (50 ml:100 ml) live diatoms were cultivated in an environment at 20 ℃ at 12: the living diatoms were cultivated with a 12h light and shade cycle (illumination: 2500 Lx). Europium-natural polysaccharide is added into diatom culture solution with good growth condition, and 100 mu L of 1×10 is added -4 The standard of moL/L is that europium-natural polysaccharide is added successively, and the europium-natural polysaccharide is added once in the morning and at night. Eu (TTA) is added by adopting the principle of a small amount of a plurality of times in the biological siliconizing process of diatom 3 phen- (Na-Hya) -Cs. Eu (TTA) is added by adopting the principle of a small amount of a plurality of times in the biological siliconizing process of diatom 3 phen- (Na-Hya) -Cs. Until 18 days of culture.
Preparation of europium-natural polysaccharide: 1mL of 1X 10 -4 EuCl of M 3 Solution and 1mL of 3X 10 -4 The TTA solution of M was stirred at 800rpm for 30min and 1mL of 1X 10 was added -4 Phen of M is reacted for 1h, then 1mL of Na-Hya is added dropwise and stirred for 1-2h, and finally 2mL of Cs is added dropwise and stirred for 1-2 h.
(2) Centrifuging the diatom suspension at 2500rpm, washing with normal saline, centrifuging for 3 times, and removing impurities; fixing the centrifuged sample with 2.5% glutaraldehyde solution, adding 4% of the sample volume according to the sample concentration, and standing at 4deg.C for 48 hr; then washing the fixed water sample with 15% -30% -50% alcohol concentration, oscillating, centrifuging to remove supernatant, repeating the operation for 3 times; and (3) placing the washed sample in an ultralow temperature refrigerator, quenching at-80 ℃, freezing, and freeze-drying to obtain the solid hybridized luminous sample.
Example 3
(1) F/2 medium was used, according to Phaeodactylum tricornutum: culture medium = 1:3 (50 ml:150 ml) live diatoms were cultivated in a 24h light and dark cycle (illumination: 3000 Lx) in an environment at 20 ℃. Europium-natural polysaccharide is added into diatom culture solution with good growth condition, and 100 mu L of 5×10 is added -3 The mols/L standard is added sequentially, once in the morning and evening. The biological siliconizing process of diatom is adopted, and the principle of small amount and multiple times is adopted for addingEu(TTA) 3 phen- (Na-Hya) -Cs. Eu (TTA) is added by adopting the principle of a small amount of a plurality of times in the biological siliconizing process of diatom 3 phen- (Na-Hya) -Cs. Until 16 days of culture.
Preparation of europium-natural polysaccharide: 1mL of 1X 10 -3 EuCl of M 3 Solution and 1mL of 3X 10 -3 The TTA solution of M was stirred at 800rpm for 30min and 1mL of 1X 10 was added -3 Phen of M is reacted for 1h, then 1mL of Na-Hya is added dropwise and stirred for 1-2h, and finally 2mL of Cs is added dropwise and stirred for 1-2 h.
(2) Centrifuging the diatom suspension at 3500rpm, washing with normal saline, centrifuging for 3 times, and removing impurities; then fixing the centrifuged sample with glycerol solution, adding 2% of the sample volume according to the sample concentration, and standing at 5 ℃ for 24 hours; then washing a fixed water sample with 30% alcohol concentration, oscillating, centrifuging to remove supernatant, and repeating the operation for 3 times; and (3) placing the washed sample in an ultralow temperature refrigerator, quenching at-80 ℃, freezing, and freeze-drying to obtain the solid hybridized luminous sample.
Example 4
(1) Using F/2 medium, according to the crescent diamond algae: medium = 1:3 (50 ml:150 ml) live diatoms were cultivated in a 15 ℃ environment at 14: the living diatoms were cultured with a light and dark cycle (light: 2000 Lx) for 10 hours. Europium-natural polysaccharide is added into diatom culture solution with good growth condition, and 200 mu L of 5×10 is added -4 The mols/L standard is added sequentially, once in the morning and evening. Eu (DBM) is added by adopting the principle of a small amount of a plurality of times in the biological siliconizing process of diatom 3 BATH- (Na-Hya) -Cs. Eu (DBM) is added by adopting the principle of a small amount of a plurality of times in the biological siliconizing process of diatom 3 BATH- (Na-Hya) -Cs. Until 25 days of culture.
Preparation of europium-natural polysaccharide: 1mL of 1X 10 -4 EuCl of M 3 Solution and 1mL of 3X 10 -4 M DBM solution was stirred at 800rpm for 30min and 1mL of 1X 10 was added -4 And (3) performing BATH reaction on M for 1h, then dropwise adding 1mL of Na-Hya, stirring for 1-2h, and finally dropwise adding 2mL of Cs, and stirring for 1-2 h.
(2) Centrifuging the diatom suspension at 3000rpm, washing with normal saline, centrifuging for 3 times, and removing impurities; then fixing the centrifuged sample with glycerol solution, adding 3% of the sample volume according to the sample concentration, and standing at 4 ℃ for 36 hours; then washing a fixed water sample with 30% alcohol concentration, oscillating, centrifuging to remove supernatant, and repeating the operation for 3 times; and (3) placing the washed sample in a refrigerator at the temperature of minus 20 ℃ for standing for 30 minutes, then placing the sample in an ultralow temperature refrigerator, freezing at the temperature of minus 80 ℃, and freeze-drying after freezing to obtain the solid hybridization luminescent sample.
Example 5
(1) Using Csi medium, according to navicular algae: medium = 1:2 (50 ml:100 ml) live diatoms were grown at a ratio of 12: the living diatoms were cultivated with a 12h light and shade cycle (illumination: 3000 Lx). Europium-natural polysaccharide is added into diatom culture solution with good growth condition, and 150 mu L of 5×10 is added -4 The mols/L standard is added sequentially, once in the morning and evening. Eu (TTA) is added by adopting the principle of a small amount of a plurality of times in the biological siliconizing process of diatom 3 BIPY- (Na-Hya) -Cs. Eu (TTA) is added by adopting the principle of a small amount of a plurality of times in the biological siliconizing process of diatom 3 BIPY- (Na-Hya) -Cs. Until cultured for 19 days.
Preparation of europium-natural polysaccharide: 1mL of 1X 10 -4 EuCl of M 3 Solution and 1mL of 3X 10 -4 The TTA solution of M was stirred at 800rpm for 30min and 1mL of 1X 10 was added -4 And (3) performing BIPY reaction on M for 1h, then dropwise adding 1mL of Na-Hya, stirring for 1-2h, and finally dropwise adding 2mL of Cs, stirring for 1-2 h.
(2) Centrifuging the diatom suspension at 3000rpm, washing with normal saline, centrifuging for 3 times, and removing impurities; fixing the centrifuged sample with 2.5% glutaraldehyde solution, adding 3% of the sample volume according to the sample concentration, and standing at 4deg.C for 36 hr; then washing the fixed water sample with 30% alcohol concentration, oscillating, centrifuging to remove supernatant, repeating the operation for 3 times; obtaining the hybridized luminescent material.
It will be understood that modifications and variations will be apparent to those skilled in the art from the foregoing description, and it is intended that all such modifications and variations be included within the scope of the following claims.
Claims (7)
1. The preparation method of the europium-natural polysaccharide doped living diatom efficient luminescent material is characterized by comprising the following steps of:
(1) Doping of luminescent living diatom: when the algae cells stably grow, europium-natural polysaccharide is added according to the principle of a small number of times: under the condition of choosing the illumination of the incubator, the method is as follows: medium = 1: (1-5) live diatom cultured in volume ratio were taken out from a cold light source incubator and put into an ultra clean bench, and 1X 10 per 50ml of algal seeds were added dropwise -4 moL/L-1×10 -3 moL/L europium-natural polysaccharide 50 muL-200 muL, adding dropwise while shaking, adjusting pH to 6.5-8.5 with acid and alkali, adding europium-natural polysaccharide dropwise once every 6-10 hours, shaking culture flask regularly, and shaking at 15-30deg.C for (12-24) h: (12-0) h of light and shade cycle cultivation of living diatom, illumination: 2000Lx-3000Lx;
(2) Obtaining a europium-natural polysaccharide doped living diatom efficient luminescent material: and (3) repeating the step (1) for 3-25 days, and then, obtaining the hybridized luminous living diatom after the living diatom suspension is treated.
2. The preparation method according to claim 1, wherein after europium-natural polysaccharide is added into the culture medium, the algae cells are split into upper and lower shells similar to a culture dish by utilizing the biological autosilicification principle of living diatom division, the other half of shells are reformed, and europium-natural polysaccharide participates in the formation of cell walls of the algae cells, so that the high-efficiency luminescent material is prepared.
3. The method of claim 1, wherein the living diatom is selected from the group consisting of a seaweed, a Mei Nixiao-loop algae, a phaeodactylum tricornutum, a rhombohedral algae, and a navicular algae.
4. The method of claim 1, wherein the europium ion, ligand and polysaccharide concentrations for preparing the europium-natural polysaccharide are: euCl 3 Solution concentration 1X 10 -4 mol/L-5×10 -3 mol/L; ligands acetylacetone (ACAC), dibenzoylmethane (DBM), methylbenzotriazole (TTA) and benzyl alcoholConcentration of Acylacetone (BA) solution 3X 10 -4 mol/L-1.5×10 -2 mol/L; 1X 10 concentration of 1, 10-Phenanthroline (PHEN), 4, 7-diphenyl-1, 10-phenanthroline (BATH), 2-Bipyridine (BIPY) and triphenylphosphine oxide (TPO) solutions -4 mol/L-5×10 -3 mol/L; sodium hyaluronate (Na-Hya) solution was 1mg/mL and chitosan (Cs) solution was 1mg/mL.
5. The method of claim 4, wherein the europium-natural polysaccharide is present in an amount of EuCl 3 ACAC: PHEN: na-Hya: cs=1:3:1:1:2; or EuCl 3 :DBM:BATH：Na-Hya：Cs＝1:3:1:1:2；EuCl 3 TTA: PHEN: na-Hya: cs=1:3:1:1:2; or EuCl 3 :BA:BIPY：Na-Hya：Cs＝1:3:1:1:2。
6. The method of preparing according to claim 1, wherein the treatment of the living diatom suspension comprises: washing with physiological saline to remove impurities; then, one or more fixed water samples in various mixed solutions prepared from glutaraldehyde, low-concentration alcohol, glycerol and the medicaments according to the proportion are selected; after fixed standing, washing residual europium-natural polysaccharide with 15% -50% alcohol; the sample was frozen in an ultra-low temperature refrigerator at-80℃and the quenched frozen sample was freeze-dried.
7. The hybrid luminescent material based on europium-doped natural polysaccharide of living diatom prepared by the method according to any one of claims 1 to 6, wherein the silicon hydroxyl groups present in living diatom and the hydroxyl groups of europium-natural polysaccharide are combined by means of covalent bonds and hydrogen bonds.
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