CN111517316A - Rare earth element labeled graphene oxide nanosheet and preparation method and application thereof - Google Patents
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Abstract
Disclosed is a rare earth element-labeled graphene oxide nanosheet, wherein a rare earth element compound is connected with the graphene oxide nanosheet through an amide bond. Also discloses a preparation method and application of the rare earth element labeled graphene oxide nanosheet. According to the invention, Graphene Oxide (GO) is functionally modified by utilizing the structural characteristics of the GO, namely the surface contains rich carboxyl, hydroxyl and epoxy groups to obtain GO modified by tetraazacyclic compounds, rare earth ion labeled GO is obtained by utilizing the strong ability of the tetraazacyclic compounds to complex rare earth element ions, a convenient and effective method can be provided for the quantitative analysis of GO in a complex system through the determination of the rare earth ions, and the problem of difficulty in the detection of the GO in a biological system is solved.
Description
Technical Field
The invention belongs to the field of biomedicine, and particularly relates to a rare earth element labeled graphene oxide nanosheet as well as a preparation method and application thereof.
Background
Graphene is the thinnest, completely two-dimensional crystal structure known, consisting entirely of carbon atoms. In recent years, graphene has a wide application prospect in various fields such as industry, biomedicine and the like due to good electrical, thermal and chemical properties. Graphene Oxide (GO) has good hydrophilicity and biocompatibility, can form stable suspension in water and other organic solvents, is easy to modify and functionalize, and can be widely applied to the fields of biosensing, biological detection, drug delivery, tumor targeted therapy and the like. However, since GO is mainly composed of C and O, quantitative analysis of GO is a difficulty in its application process.
Currently common methods for GO quantification include radioelement tracing (e.g., by radioactive element tracing)125I or111In or14C) Fluorescence labeling and raman spectroscopy, however the radiolabelling approach is limited to specialized radiochemical laboratory conditions; the raman scattering effect is a very weak process, and due to the interference of an environmental complex system on a fluorescence signal, the raman signal of GO in the complex system is very weak, and therefore, GO is difficult to be used for quantitative analysis. The fluorescent signal of the fluorescent molecular labeling method is easily quenched by GO, and the requirement of detection in a biological complex system cannot be well met.
Disclosure of Invention
In order to overcome the defects, the invention provides a rare earth element labeled graphene oxide nanosheet, and a preparation method and application thereof.
The invention provides a rare earth element labeled graphene oxide nanosheet, wherein a rare earth element compound is connected with the graphene oxide nanosheet through an amido bond.
According to an embodiment of the present invention, the rare earth element compound is composed of a rare earth element ion and a tetraazacyclo having a thiocyanate group.
According to another embodiment of the invention, the amide bond is formed by coupling aminated polyethylene glycol connected to the graphene oxide nanosheets and a thiocyanate group of the rare earth element compound, and the molecular weight of the aminated polyethylene glycol is 5000-20000 Da.
According to another embodiment of the invention, the rare earth element is selected from one or more of lanthanum, neodymium, samarium, europium, gadolinium, ytterbium, lutetium.
According to another embodiment of the invention, the content of rare earth elements is between 45.6ppt and 44.2 ppm.
According to another embodiment of the present invention, the height of the nanosheet is 0.8 to 1.2nm, and the diameter of the nanosheet is 70 to 100 nm.
The invention also provides a preparation method of the rare earth element labeled graphene oxide nanosheet, which comprises the following steps: s1, modifying carboxyl to graphene oxide nanosheets to form carboxyl-modified graphene oxide nanosheets; s2, coupling carboxyl modified on the graphene oxide nanosheets with aminated polyethylene glycol through an amide reaction to form polyethylene glycol modified graphene oxide nanosheets; s3, coupling the tetraazacyclo compound with the thiocyanate group and the graphene oxide modified with the aminated polyethylene glycol through a C-N bond to obtain a tetraazacyclo compound modified graphene oxide nanosheet; and S4, mixing and reacting the graphene oxide nanosheet modified by the tetraazacyclo compound with an aqueous solution containing the rare earth element to obtain the rare earth element-labeled graphene oxide nanosheet.
According to an embodiment of the invention, the step S1 is preceded by a step of separating and purifying graphene oxide nanosheets, and graphene oxide nanosheets with a flake diameter of 70-100 nm are obtained by subjecting graphene oxide with an initial flake diameter of 10-1000 nm to ultrasonic and centrifugal methods.
According to another embodiment of the invention, the rare earth element is selected from one or more of lanthanum, neodymium, samarium, europium, gadolinium, ytterbium, lutetium.
The invention also provides application of the rare earth element labeled graphene oxide nanosheet in biosensing, biological detection, medicines or tumor treatment.
According to the invention, Graphene Oxide (GO) is functionally modified by utilizing the structural characteristics of the GO, namely the surface contains rich carboxyl, hydroxyl and epoxy groups to obtain GO modified by tetraazacyclic compounds, rare earth ion labeled GO is obtained by utilizing the strong ability of the tetraazacyclic compounds to complex rare earth element ions, a convenient and effective method can be provided for the quantitative analysis of GO in a complex system through the determination of the rare earth ions, and the problem of difficulty in the detection of the GO in a biological system is solved.
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The above and other features and advantages of the present invention will become more apparent by describing in detail exemplary embodiments thereof with reference to the attached drawings.
Fig. 1 is a flowchart of preparing a rare earth element-labeled graphene oxide nanosheet according to an embodiment of the present invention.
FIG. 2 is an infrared spectrum of the product of each step in the Yb labeling of GO prepared in example 1.
FIG. 3 is a TEM image of Yb-labeled GO prepared in example 1.
Fig. 4 is an atomic force imaging plot of Yb-labeled GO prepared in example 1.
Fig. 5 is a graph showing the time-varying morphology of Yb-labeled GO prepared in example 1 in physiological saline.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
According to the rare earth element labeled graphene oxide nanosheet, the rare earth element compound is connected with the graphene oxide nanosheet through an amido bond. The rare earth element labeling strategy shows wide application prospect in the aspect of immunodetection of protein, polypeptide and the like. By marking rare earth elements on the graphene oxide nanosheets, quantitative analysis of the graphene oxide in a complex system can be realized.
The GO surface contains rich carboxyl, hydroxyl and epoxy groups, can be coupled with an N heterocyclic compound, and is marked through stronger complexing ability of the N heterocyclic compound and rare earth ions. The N heterocyclic compound is preferably a tetraazacyclic compound (DOTA) with a thiocyanate group, and an amido bond is formed by coupling the thiocyanate group and an amino group on the graphene oxide nanosheet. Therefore, the rare earth element compound connected to the graphene oxide nanosheet is composed of rare earth element ions and a tetraazacyclo having a thiocyanate group. The amino groups on the graphene oxide nanoplatelets can be derived from modifying the graphene oxide nanoplatelets by aminated polyethylene glycol. Preferably, the molecular weight of the aminated polyethylene glycol is 5000-20000 Da. The kidney clearance of the PEG molecule is gradually reduced along with the increase of the molecular weight of the aminated polyethylene glycol, and when the molecular weight is more than 20000, the kidney clearance of the PEG molecule is obviously reduced. The upper limit of the molecular weight of the aminated polyethylene glycol is preferably 20000 in view of safety of PEG in vivo.
The amido bond formed by the rare earth compound composed of the aminated polyethylene glycol modified on the graphene oxide nanosheet, the tetraazacyclo having a thiocyanate group and the rare earth element is taken as an example to explain one way of connecting the rare earth element compound with the graphene oxide nanosheet through the amido bond. However, any method of linking the rare earth element compound to the graphene oxide nanosheet through an amide bond is within the scope of the present invention.
In a preferred embodiment of the invention, the rare earth element is selected from one or more of lanthanum, neodymium, samarium, europium, gadolinium, ytterbium, lutetium. The higher the content of the rare earth element in the rare earth element-labeled graphene oxide nanosheet is, the more detection is facilitated, so the lower limit of the content of the rare earth element is 45.6ppt which can be detected by an instrument, and the upper limit of the content of the rare earth element is 44.2ppm which can be labeled by the rare earth element, so that the content of the original rare earth element is 45.6 ppt-44.2 ppm. One skilled in the art can select any value from 45.6ppt to 44.2ppm according to actual needs.
The rare earth element labeled graphene oxide nanosheet is preferably nanosheet with a height of 0.8-1.2 nm and a diameter of 70-100 nm. The height of the nanosheets is 0.8-1.2 nm, namely the nanosheets are single-layer, stacking of the nanosheets can be avoided, the nanosheets are prevented from being blocked in a blood vessel, and thrombus is avoided from being formed. Due to the restriction of biological blood vessels, the diameter of the nanosheet is preferably 70-100 nm.
The rare earth element-labeled graphene oxide nanoplatelets of the present invention may be prepared by steps S1, S2, S3 and S4 for distinguishing the respective steps only, and any necessary auxiliary steps such as washing, purification, etc. may be further included therebetween. The preparation process comprises the following steps: s1, modifying carboxyl to graphene oxide nanosheets to form carboxyl-modified graphene oxide nanosheets; s2, coupling carboxyl modified on the graphene oxide nanosheets with aminated polyethylene glycol through an amide reaction to form polyethylene glycol modified graphene oxide nanosheets; s3, coupling the tetraazacyclo compound with the thiocyanate group and the graphene oxide modified with the aminated polyethylene glycol through a C-N bond to obtain a tetraazacyclo compound modified graphene oxide nanosheet; and S4, mixing and reacting the graphene oxide nanosheet modified by the tetraazacyclo compound with an aqueous solution containing the rare earth element to obtain the rare earth element-labeled graphene oxide nanosheet.
FIG. 1 shows an example of a rare earth element Yb and a tetraazacyclic compound 2- [ (4-isothiocyanatophenyl) methyl ] -1,4,7, 10-tetraazacyclododecane-1, 4,7, 10-tetraacetic acid (p-NCS-Bn-DOTA) to explain the inventive concept of forming rare earth element labeled graphene oxide nanosheets according to the present invention.
In step S1, a carboxyl group is modified to graphene oxide nanoplatelets to form carboxyl group-modified graphene oxide nanoplatelets. Adding predetermined amounts of sodium hydroxide and chloroacetic acid (the addition amount of the sodium hydroxide and the chloroacetic acid can be selected according to the content of the carboxyl group to be modified) into the aqueous dispersion of GO, stirring for 8-12 h at room temperature, dialyzing at room temperature, then performing centrifugal separation, collecting the precipitate, and re-dispersing into water to obtain the carboxyl group modified graphene oxide (GO-COOH). The water is 18.2M omega ultrapure water, and the pH value of the reaction system is more than 12.0 (preferably 13-13.5).
In the step S2, carboxyl modified on the graphene oxide nanosheets is coupled with aminated polyethylene glycol through an amide reaction to form polyethylene glycolA graphene oxide nanoplatelet modified with diol. The method specifically comprises the following steps: performing ultrasonic dispersion on GO-COOH dispersion liquid obtained in the step S1 in a room-temperature water bath, then adding aminated polyethylene glycol and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride after a period of time, stirring for 8-12 h at room temperature, performing centrifugal separation on the obtained product, collecting precipitate, performing vortex and ultrasonic re-dispersion on the precipitate into water to obtain amino polyethylene glycol modified graphene oxide (GO-PEG-NH)2). The water used was 18.2 M.OMEGA.ultrapure water, pH 7.0.
In the step S3, a tetraazacyclo compound with a thiocyanate group is coupled with graphene oxide modified with aminated polyethylene glycol through a C-N bond to obtain a tetraazacyclo compound modified graphene oxide nanosheet. The method specifically comprises the following steps: sodium bicarbonate is used for dissolving GO-PEG-NH obtained in the step S32And (3) adding NCS-DOTA into the dispersion liquid with the pH value of about 7.0-7.4 (preferably the pH value of 7.2), stirring at room temperature for 24-48 h, dialyzing, centrifugally separating the obtained product, collecting precipitates, and re-dispersing into water to obtain DOTA-GO-PEG.
And S4, mixing and reacting the graphene oxide nanosheet modified by the tetraazacyclo compound with an aqueous solution containing the rare earth element to obtain the rare earth element-labeled graphene oxide nanosheet. The method specifically comprises the following steps: adding ytterbium nitrate into the DOTA-GO-PEG dispersion liquid obtained in the step S3, stirring, dialyzing, centrifugally separating, collecting precipitate, and re-dispersing into water to obtain (DOTA-GO-PEG)Yb。
Before modifying the graphene oxide carboxyl, namely before the step of S1, GO can be separated and purified to obtain graphene oxide nanosheets of uniform size. Specifically, GO with the sheet diameter size of 10-1000 nm can be selected as a raw material, and GO nano sheets with the sheet diameter size of 70-100 nm are obtained through an ultrasonic and centrifugal method, so that rare earth element labeled graphene oxide nano sheets with the preset size can be obtained.
The rare earth element labeled graphene oxide nanosheet can be widely applied to biosensing, biological detection, medicines or tumor treatment.
The inventive concept of the present invention is explained in detail below with reference to specific embodiments. The experimental procedures used in the following examples are all conventional procedures unless otherwise specified. Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1
Separation and purification of GO
GO lamella with the lamella diameter of 10-1000 nm is selected as a raw material, and GO nanosheets with the lamella diameter of 70-100 nm are obtained through probe type ice bath ultrasound and step-by-step centrifugation.
The ultrasonic power of the probe type ultrasonic instrument is 500W, and the working mode is that the interval is 5s after the operation is 5 s. The total time of ultrasonication was 12 h.
The step-by-step centrifugation is three-stage separation, and the rotating speed is respectively set to be 5000-7000 rpm, 9000-11000 rpm and 12000-14000 rpm.
Carboxylated modification of GO
Stirring 10mL and 2mg/mL of the separated and purified GO in the water dispersion for 12 hours at the rotating speed of 500 rpm. 1.2g of sodium hydroxide and 1.0g of chloroacetic acid were dissolved in 2mL of water, respectively, to ensure a pH of 13.5. The sodium hydroxide solution was cooled to room temperature of 22 ℃ and added to the dispersion. Then, chloroacetic acid solution was added under stirring, and stirred at room temperature 22 ℃ for 8h, and the resulting precipitate was passed through a vortex for 30s and water bath at 25 ℃ for 15min with ultrasound. And dialyzing the obtained carboxylated graphene oxide at room temperature of 22 ℃ for 48 hours to remove excessive sodium hydroxide, chloroacetic acid and sodium salt generated by reaction, wherein the size of a dialysis bag is 70mm, and the length of the dialysis bag is 5 cm. Followed by centrifugation at 14000rpm for 10 min. And collecting the precipitate, and re-dispersing the precipitate into 10mL of water to obtain carboxyl modified graphene oxide (GO-COOH). The water used was 18.2 M.OMEGA.ultrapure water.
Polyethylene glycol modification of GO-COOH
5mL of the obtained GO-COOH dispersion liquid is taken, 5mL of water is added, and water bath ultrasound (ultrasound frequency 40kHz, ultrasound power 400W) is carried out at room temperature and 22 ℃ for 30 min. 50mg of aminated polyethylene glycol was added, and then 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride was added in two portions in a mass of 10mg and 40mg, respectively. Wherein, the amino polyethylene glycol and the 1- (3-dimethylamino propyl group) The 3-ethyl carbodiimide hydrochloride is dissolved in 1mL of water, added to the dispersion with stirring, and stirred at room temperature for 12 h. Centrifuging the obtained product at 14000rpm for 15min to obtain precipitate, dispersing the precipitate in 5mL of water again by vortex and ultrasound to obtain amino polyethylene glycol modified graphene oxide (GO-PEG-NH)2. The water used was 18.2M Ω ultrapure water, pH 7.0.
2DOTA modified GO-PEG-NH
Taking the obtained GO-PEG-NH25mL of the dispersion was added, and the pH of the system was adjusted to 7.2 with sodium bicarbonate. 5.0mg of 2- [ (4-isothiocyanatophenyl) methyl group were taken]-1,4,7, 10-tetraazacyclododecane-1, 4,7, 10-tetraacetic acid (p-NCS-Bn-DOTA) was dissolved in 0.1mL of water to form a DOTA solution. Adding DOTA solution to GO-PEG-NH2In the dispersion, the reaction was carried out for 24h and the product obtained was dialyzed for 24h to remove unreacted DOTA molecules. The resulting product was centrifuged at 14000rpm for 10min, the precipitate collected and redispersed in 10mL of water to give DOTA-GO-PEG.
Complexation of DOTA-GO-PEG with rare earth ions
And taking 5mL of the obtained DOTA-GO-PEG dispersion liquid, adding ytterbium nitrate at 60 ℃, wherein the addition amount of the ytterbium nitrate is 1mmol/mL, and the reaction time is 4 h. Naturally cooling to room temperature after the reaction is finished, dialyzing the obtained product at room temperature of 22 ℃ for 24h, centrifuging at 14000rpm for 10min, collecting precipitate, and re-dispersing into 5mL of water to obtain (DOTA-GO-PEG)Yb。
FIG. 2 shows the infrared spectra of the reaction products obtained in the respective steps. The GO-COOH spectrogram shows that C is equal to C (1626 cm)-1)、C-OH(3344cm-1)、C＝O(1722cm-1) And C-O-C (1074 cm)-1) The stretching vibration peak shows that the graphene oxide nanosheet (GO-COOH) modified by carboxyl contains hydroxyl, carboxyl, epoxy group and the like. From the PEG characterization result, PEG presents several obvious characteristic peaks, which are 2950cm respectively-1nearby-CH2and-CH3Peak of stretching vibration, 1400cm-1Left and right C-N stretching vibration peaks at 1350cm-1NH of (C)2Peak sum 1250cm-1Characteristic peak of C-O-C. GO-PEG-NH2In the spectrogram, at 1600cm-1(CO-NH) newly appearedThe peak indicates that PEG has been successfully covalently modified to GO. While the enhancement and right shift of the carboxyl peak in the DOTA-PEG-GO spectrogram indicate that DOTA has been successfully combined with GO-PEG-NH2The above.
From the TEM image of FIG. 3, the sheet size of the product obtained in example 1 was 272. + -.95 nm and the Zeta potential was-19.6. + -. 0.1 mV.
The marking rate of Yb measured by ICP-MS can reach 35.8 mg/g.
Fig. 4 is an atomic force imaging plot of Yb-labeled GO prepared in example 1. As can be seen from FIG. 4, the average thickness of the material is 0.95. + -. 0.35nm, the size of the material is uniform, and the material has good dispersibility.
Fig. 5 is a graph showing the time-varying morphology of Yb-labeled GO prepared in example 1 in physiological saline. As can be seen from the photographs, the product was stable in the normal saline system for at least 7 days.
The detailed physicochemical characterization of the product is given in table 1.
TABLE 1
| Physical and chemical properties | (DOTA-GO-PEG)Yb |
| Average size (nm) | 272±95 |
| Hydrodynamic diameter (nm) | 381.3±9.9 |
| Zeta potential (mV) | -19.6±0.1 |
| Marking efficiency (mg/g) | 35.8±1.0 |
| Stability of the Label (%) | 99.0±2.0 |
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (10)
1. A rare earth element labeled graphene oxide nanosheet is characterized in that a rare earth element compound is connected with the graphene oxide nanosheet through an amido bond.
2. Rare earth element-labeled graphene oxide nanoplatelets according to claim 1 wherein the rare earth element compound is composed of rare earth element ions and tetraazacyclo having a thiocyanate group.
3. The rare earth element-labeled graphene oxide nanoplatelets of claim 2 wherein the amide bond is formed by coupling an aminated polyethylene glycol having a molecular weight of 5000-20000 Da attached to the graphene oxide nanoplatelets with a thiocyanate group of the rare earth element compound.
4. Rare earth element-labeled graphene oxide nanoplatelets according to claim 1 wherein the rare earth element is selected from one or more of lanthanum, neodymium, samarium, europium, gadolinium, ytterbium, lutetium.
5. Rare earth element-labeled graphene oxide nanoplatelets according to claim 1 wherein the rare earth element content is between 45.6ppt and 44.2 ppm.
6. A rare earth element-labeled graphene oxide nanoplatelet according to claim 1 wherein the nanoplatelet has a height of 0.8 to 1.2nm and a diameter of 70 to 100 nm.
7. A preparation method of a rare earth element-labeled graphene oxide nanosheet is characterized by comprising the following steps:
s1, modifying carboxyl to graphene oxide nanosheets to form carboxyl-modified graphene oxide nanosheets;
s2, coupling carboxyl modified on the graphene oxide nanosheets with aminated polyethylene glycol through an amide reaction to form polyethylene glycol modified graphene oxide nanosheets;
s3, coupling the tetraazacyclo compound with the thiocyanate group and the graphene oxide modified with the aminated polyethylene glycol through a C-N bond to obtain a tetraazacyclo compound modified graphene oxide nanosheet; and
and S4, mixing and reacting the graphene oxide nanosheet modified by the tetraazacyclo compound with an aqueous solution containing the rare earth element to obtain the rare earth element-labeled graphene oxide nanosheet.
8. The preparation method of rare earth element-labeled graphene oxide nanosheets according to claim 7, further comprising a step of separating and purifying the graphene oxide nanosheets before the step of S1, wherein the graphene oxide nanosheets with the initial flake diameter of 10-1000 nm are obtained by subjecting graphene oxide with the initial flake diameter of 70-100 nm to ultrasonic and centrifugal modes.
9. The method of preparing a rare earth-labeled graphene oxide nanoplatelet of claim 7 wherein the rare earth element is selected from one or more of lanthanum, neodymium, samarium, europium, gadolinium, ytterbium, lutetium.
10. Use of rare earth element-labeled graphene oxide nanoplatelets according to any of claims 1-6 in biosensing, biodetection, medicine or treatment of tumors.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140227163A1 (en) * | 2011-05-11 | 2014-08-14 | Brookhaven Science Associates, Llc | Processing of Monolayer Materials Via Interfacial Reactions |
| CN104436221A (en) * | 2013-09-23 | 2015-03-25 | 中国科学院苏州纳米技术与纳米仿生研究所 | Grapheme-oxide based contrast agent and preparation method thereof |
| CN105797174A (en) * | 2016-01-22 | 2016-07-27 | 复旦大学附属肿瘤医院 | Nanometer graphene oxide-based magnetic resonance imaging contrast agent and preparation method thereof |
| WO2019020999A1 (en) * | 2017-07-26 | 2019-01-31 | Talga Technologies Limited | Functionalised graphene composition |
| CN109678143A (en) * | 2019-03-04 | 2019-04-26 | 吉林大学 | Hyperbranched rare earth phthalocyanine modification graphene oxide and its preparation and the application in lasing safety |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140227163A1 (en) * | 2011-05-11 | 2014-08-14 | Brookhaven Science Associates, Llc | Processing of Monolayer Materials Via Interfacial Reactions |
| CN104436221A (en) * | 2013-09-23 | 2015-03-25 | 中国科学院苏州纳米技术与纳米仿生研究所 | Grapheme-oxide based contrast agent and preparation method thereof |
| CN105797174A (en) * | 2016-01-22 | 2016-07-27 | 复旦大学附属肿瘤医院 | Nanometer graphene oxide-based magnetic resonance imaging contrast agent and preparation method thereof |
| WO2019020999A1 (en) * | 2017-07-26 | 2019-01-31 | Talga Technologies Limited | Functionalised graphene composition |
| CN109678143A (en) * | 2019-03-04 | 2019-04-26 | 吉林大学 | Hyperbranched rare earth phthalocyanine modification graphene oxide and its preparation and the application in lasing safety |
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