Preparation and detection method of fluorescent specialty paper for rapidly detecting Fe < 3 + > in environment
By preparing fluorescent special paper mixed with nanocellulose crystals and dissolved slurry fibers, the problems of complex traditional detection methods and high material toxicity are solved, and fast, accurate and low-cost Fe3+ detection is achieved.
Patent Information
- Application Number
- CN202510505315.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-15
- Publication Date
- 2025-08-01
AI Technical Summary
The prior art is difficult to achieve fast, simple and environmentally friendly iron ion Fe3+ detection. Traditional methods rely on precision instruments and cumbersome operations, and traditional fluorescent sensing materials have low biocompatibility, high toxicity and high cost.
The nanocellulose crystals were mixed with dissolved slurry fibers to prepare fluorescent special paper, and Fe3+ was detected by ultraviolet excitation, and quantitative analysis was performed using fluorescence intensity changes.
It realizes fast and accurate Fe3+ detection, with a mild process that is free from environmental pollution, low cost, simple operation, and high selectivity and linear response.
Smart Images
Figure CN120401267A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to a method for rapidly detecting Fe 3+ The invention discloses a preparation and detection method of fluorescent special paper, belonging to the technical field of functional material preparation and application. Background Art Iron is one of the most important trace elements in biological systems, playing an irreplaceable role in biological metabolism. Excessive iron in the human body produces excessive oxygen free radicals, which can cause serious damage to the body. In daily life, excessive discharge of industrial wastewater and over-mining can affect environmental safety and soil health, and indirectly accumulate in ecosystems through the food chain, entering the human body and causing harm. Traditional detection methods include atomic absorption spectroscopy (AAS), inductively coupled plasma mass spectrometry (ICP-MS), colorimetry, photometry, and voltammetry. Although these methods are highly sensitive, they rely on precision instruments, cumbersome pre-treatment processes, and professional operation thresholds, making it difficult to achieve real-time monitoring and on-site rapid analysis. In contrast, fluorescence sensing technology has become a popular method for Fe detection in recent years due to its advantages such as simple operation, fast response, low cost, and visual detection. 3+ It is a research hotspot in the detection field. It mainly converts the specific binding process of target ions and fluorescent substances into observable light signal changes through mechanisms such as photoinduced electron transfer (PET), intramolecular charge transfer (ICT) and chelation enhanced fluorescence (CHEF). Existing fluorescent sensing materials generally use organic solvent systems, which have problems such as low biocompatibility, high toxicity and high cost. Therefore, the development of new fluorescent materials that are environmentally friendly, functional and easy to process has become a hot topic in Fe 3+ An important breakthrough direction in the field of sensing. In this context, cellulose, as the most abundant natural polymer in nature, has been widely used in the development of fluorescent sensing materials in recent years due to its renewability, biodegradability and excellent chemical modifiability. The abundant hydroxyl (-OH) and derivatizable carboxyl (-COOH), amino (-NH2) and other functional groups in the cellulose molecular chain can be used to introduce fluorescent groups (such as rhodamine, naphthalimide, carbon quantum dots, etc.) through esterification, etherification or graft copolymerization reactions to construct multifunctional sensing materials. These materials can not only accurately identify specific chemicals or biomolecules, but also sensitively perceive changes in environmental parameters. This has opened up innovative avenues for the development of intelligent detection devices and can respond to environmental changes, providing new possibilities for scientific research and practical applications. Summary of the Invention
[0002] Based on the above factors, the present invention provides a method for simply and quickly detecting Fe 3+Preparation and detection method of fluorescent special paper. First, a nanocrystalline cellulose with fluorescence characteristics was prepared, and then it was mixed with dissolving pulp fibers to prepare a transparent fluorescent special paper. This special paper can rapidly and effectively detect Fe 3+ rapidly and effectively.
[0003] Technical solution of the present invention: A preparation and detection method of a fluorescent special paper for rapidly detecting Fe 3+ in the environment, comprising the following steps:
[0004] (1) Preparation of fluorescent reagent: Cellulose fibers are subjected to periodate aldehyde modification, hydrogen bond dissociation and amination in a guanidine salt / organic acid green solvent for dialdehyde cellulose and coupled with high-pressure homogenization to obtain cationic nanocrystalline cellulose with ultra-low size and fluorescence.
[0005] (2) Preparation of fluorescent paper: The dissolving pulp is beaten with a PFI to obtain dissolving pulp fibers with a certain beating degree, and then mixed with the fluorescent reagent obtained in step (1) in a certain mass ratio, stirred evenly, filtered by suction, and pressed and dried to obtain the fluorescent special paper.
[0006] (3) Using the fluorescent special paper obtained in step (2) as a test paper, 1 mL of different metal ion solutions are dropped on the fluorescent special paper strip, and then left to stand and dry for 5 - 10 min. The fluorescence intensity F0 of the fluorescent special paper without adding metal ions and the fluorescence intensity F of the fluorescent special paper after adding metal ions are measured at a fixed excitation wavelength of 365 nm, and the change curve of the fluorescence intensity at this laser wavelength is plotted.
[0007] (4) Using the fluorescent special paper obtained in step (2) as a test paper, 1 mL of Fe 3+ solutions with different concentrations are dropped on the fluorescent special paper strip, and then left to stand and dry for 5 - 10 min. Fluorescence emission spectroscopy is carried out at a fixed excitation wavelength of 365 nm, and the change of the fluorescence intensity of the fluorescent special paper is recorded.
[0008] Preferably, in step (1), the cellulose fibers are dissolving pulp, cotton pulp, microcrystalline cellulose, etc., the guanidine salts are aminoguanidine hydrochloride, guanidine hydrochloride, guanidinoacetic acid, etc., and the organic acids are lactic acid, formic acid, citric acid, etc.
[0009] Preferably, in step (1), the mass ratio of aminoguanidine hydrochloride / lactic acid solvent to dialdehyde cellulose is 20:1, the reaction temperature is 70 - 110 °C, and the reaction time is 1 - 3 h.
[0010] Preferably, in step (2), the beating degree of the dissolving pulp is 40 - 80 °SR.
[0011] Preferably, in the step (2), the mass ratio of the dissolving pulp fiber to the cationic nanocellulose crystal is 1:1, 1:2, 1:3, 1:4, 1:5, and the reaction temperature is room temperature.
[0012] Preferably, in the step (3), the different metal ion solutions include Na + , Ni 2+ , Li + , Ba + , Mn 2+ , Cu 2+ , Mg 2 + , Zn 2+ , Co 2+ , Zr 4+ , Ca 2+ , Al 3+ and Fe 3+ 13 kinds of metal ions, and the preparation concentrations of the above metal ions are all 30 μmol / L.
[0013] Preferably, in the step (4), Fe 3+ exists in the form of FeCl3 and Fe2(SO4)3, etc., and the solution concentration range is 10 - 100 μmol / L.
[0014] The present invention discloses the following technical effects:
[0015] The fluorescent special paper prepared by the present invention can rapidly and accurately detect Fe 3+ . The whole preparation process has mild conditions, no pollution to the environment, and has advantages such as low cost and simple operation.
[0016] The fluorescent special paper has high selectivity for Fe 3+ , and its fluorescence intensity shows a linear relationship with the concentration of Fe 3+ within the range of 10 - 100 μmol / L. Description of the Drawings
[0017] Figure 1 is a physical picture of the fluorescent special paper;
[0018] Figure 2 is a fluorescence effect picture of the fluorescent special paper;
[0019] Figure 3 is a fluorescence intensity picture of the fluorescent special paper for different metal ions;
[0020] Figure 4 is the sensitivity of the fluorescent special paper to different metal ions;
[0021] Figure 5 is a physical picture of the specific selectivity of the fluorescent special paper for Fe 3+ ;
[0022] Figure 6 is the fluorescence intensity change curve of fluorescent special paper for different Fe 3+ concentrations;
[0023] Figure 7 is the linear relationship diagram between the fluorescence intensity of fluorescent special paper and Fe 3+ concentration;
[0024] Figure 8 is the fluorescence detection effect diagram of fluorescent reagent for different forms of Fe 3+ ;
[0025] Figure 9 is the detection diagram of Fe by fluorescent special paper prepared by adding different fluorescent reagents 3+ . Specific embodiments
[0026] The present invention will be further described below in conjunction with specific embodiments. It should be understood that the described embodiments are only a part of the embodiments of the present invention, not all of the embodiments. Those skilled in the art can make appropriate modifications or supplements to the present invention, but all fall within the scope of the claims set by the present invention.
[0027] Example 1
[0028] A preparation and detection method of a fluorescent special paper for rapidly detecting Fe in the environment 3+ comprises the following steps:
[0029] (1) 5 g of microcrystalline cellulose is aldehyde-functionalized with periodate to obtain dialdehyde cellulose, and then undergoes hydrogen bond dissociation and amination under the action of aminoguanidine hydrochloride / lactic acid solvent. The reaction temperature is 90 °C, the reaction time is 2 h, and high-pressure homogenization is coupled to obtain ultra-low size cationic nanocellulose crystals with fluorescence properties.
[0030] (2) The dissolving pulp is beaten with PFI to obtain dissolving pulp fibers with 60° SR, and then mixed with the fluorescent reagent obtained in step (1) in a ratio of 1:3, stirred evenly at room temperature, filtered, and pressed and dried to obtain fluorescent special paper (as Figure 1 shown).
[0031] (3) The fluorescent special paper prepared in step (2) emits strong blue fluorescence under ultraviolet light irradiation, as Figure 2 shown.
[0032] (4) Selectivity experiment of the fluorescent special paper prepared in step (2) for different metal ions:
[0033] The present invention selects Na + , Ni 2+ , Li+ 、 Ba + 、 Mn 2+ 、 Cu 2+ 、 Mg 2+ 、 Zn 2+ 、 Co 2+ 、 Zr 4+ 、 Ca 2+ 、 Al 3 + and Fe 3+ Thirteen metal ions. The prepared concentrations of the above metal ions are all 30 μmol / L. Drop 1 mL of them onto the fluorescent special paper prepared in Example 1, then let it stand and dry for 5 - 10 min. Measure the fluorescence intensity F0 of the fluorescent special paper without added metal ions and the fluorescence intensity F of the fluorescent special paper after adding metal ions at the fixed excitation wavelength of 365 nm, and draw the change curve of the fluorescence intensity at this laser wavelength to study the selectivity of the fluorescent special paper for metal ions.
[0034] As Figure 3 、 4 shown, the fluorescent special paper prepared in Example 1 has the most obvious fluorescence quenching effect on Fe 3+ and the highest selectivity for Fe 3+ . Adding a mixture of different metal ions to the same fluorescent special paper still has the fluorescence quenching effect, as Figure 5 shown.
[0035] Example 2
[0036] A preparation and detection method of a fluorescent special paper for rapid detection of Fe 3+ in the environment, including the following steps:
[0037] (1) After subjecting 5 g of microcrystalline cellulose to periodate aldehyde group modification, dialdehyde cellulose is obtained, and then hydrogen bond dissociation and amination occur under the action of an aminoguanidine hydrochloride / lactic acid solvent. The reaction temperature is 90 °C, the reaction time is 2 h, and high-pressure homogenization is coupled to obtain ultra-low-sized cationic nanocellulose crystals with fluorescence properties.
[0038] (2) Pulp the dissolving pulp with PFI to obtain dissolving pulp fibers with 60° SR, and then mix them with the fluorescent reagent obtained in step (1) at a ratio of 1:3, stir evenly at room temperature, filter by suction, and press and dry to obtain the fluorescent special paper.
[0039] (3) The fluorescent special paper prepared in step (2) emits strong blue fluorescence under ultraviolet lamp irradiation.
[0040] (4) The fluorescent special paper prepared in step (2) is used for the Fe 3+ concentration experiment:
[0041] Prepare Fe 3+ For the aqueous solution to be measured, the gradients are 10 μmol / L, 20 μmol / L, 30 μmol / L, 40 μmol / L, 50 μmol / L, 60 μmol / L, 70 μmol / L, 80 μmol / L, 90 μmol / L, and 100 μmol / L respectively. Then, it is dropped onto the fluorescent special paper prepared in Example 2, and the dropping amount is 1 mL. Subsequently, it is left to stand and dry for 5 - 10 min, and the fluorescence emission spectrum is measured with an excitation wavelength of 365 nm fixed, and the change in the fluorescence intensity of the fluorescent special paper is recorded.
[0042] (5) Detection experiment of the fluorescent reagent prepared in step (1) for different forms of Fe 3+ :
[0043] Take 2 mL of the fluorescent reagent, and add 100 μL of Fe in the forms of FeCl3 and Fe2(SO4)3 with a concentration of 30 μmol / L respectively 3+ solution, irradiate it with an ultraviolet lamp, and observe the change in its fluorescence intensity.
[0044] The fluorescence spectrum diagram between the fluorescence intensity of the fluorescent special paper prepared in Example 2 and the Fe 3+ concentration is as shown in Figure 6 . When the Fe 3+ concentration is between 10 - 100 μmol / L, there is a linear relationship between the fluorescence intensity of the composite fluorescent special paper and the Fe 3+ concentration, as shown in Figure 7 . The prepared fluorescent reagent shows a fluorescence quenching effect after adding equal amounts of Fe in the forms of FeCl3 and Fe2(SO4)3 with the same concentration, as shown in 3+ . Figure 8
[0045] Example 3
[0046] A preparation and detection method for a fluorescent special paper for rapidly detecting Fe in the environment 3+ , which includes the following steps:
[0047] (1) After subjecting 5 g of microcrystalline cellulose to periodate aldehyde group modification, dialdehyde cellulose is obtained. Then, under the action of an aminoguanidine hydrochloride / formic acid solvent, hydrogen bond dissociation and amination occur. The reaction temperature is 90 °C, the reaction time is 1 h, and high-pressure homogenization is coupled to obtain ultra-low-sized cationic nanocellulose crystals with fluorescence properties.
[0048] (2) Pulp the dissolving pulp with PFI to obtain dissolving pulp fibers with a beating degree of 60°SR. Then, mix them with the fluorescent reagent obtained in step (1) at a ratio of 1:3, stir evenly at room temperature, filter, press, and dry to obtain the fluorescent special paper.
[0049] (3) Add 1 mL of 30 μmol / L Fe 3+ solution to the fluorescent special paper prepared in step (2), then let it stand and dry for 5 - 10 min, and observe the change in its fluorescence intensity under ultraviolet light irradiation.
[0050] The fluorescent special paper prepared in Example 3 showed a fluorescence quenching effect after adding Fe 3+ solution, as Figure 9 shown.
Claims
1. A method for preparing and detecting a fluorescent special paper for rapidly detecting Fe in the environment 3+ , characterized in that It includes the following steps: Step (1) Preparation of fluorescent reagent: Cellulose fibers are aldehyde-functionalized with periodate, the hydrogen bonds in dialdehyde cellulose are dissociated by guanidine salt / organic acid green solvent and aminated, and then coupled with high-pressure homogenization to obtain ultra-low-sized cationic fluorescent nanocellulose crystals. Step (2) Preparation of fluorescent paper: Dissolving pulp is beaten with PFI to obtain dissolving pulp fibers with a certain beating degree, and then mixed with the fluorescent reagent obtained in step (1) at a certain mass ratio, stirred evenly, filtered by suction, and pressed and dried to obtain fluorescent special paper. Step (3) Using the fluorescent special paper obtained in step (2) as a test strip, 1 mL of different metal ion solutions are dropped on the fluorescent special paper strip, and then left to stand and dry for 5 - 10 min. The fluorescence intensity F0 of the fluorescent special paper without added metal ions and the fluorescence intensity F of the fluorescent special paper after adding metal ions are measured at a fixed excitation wavelength of 365 nm, and the change curve of the fluorescence intensity at this laser wavelength is plotted. Step (4): Use the fluorescent special paper obtained in step (2) as a test strip, and drop 1 mL of Fe solutions with different concentrations on the test strip of the fluorescent special paper. Then leave it to stand and dry for 5 - 10 min, and perform fluorescence emission spectrum measurement with a fixed excitation wavelength of 365 nm, and record the change in fluorescence intensity of the fluorescent special paper. 3+ 2. A method for preparing and detecting a fluorescent special paper for rapidly detecting Fe in the environment according to claim 1 3+ , characterized in that In step (1), the cellulose fibers are dissolving pulp, cotton pulp, microcrystalline cellulose, etc., the guanidine salts are aminoguanidine hydrochloride, guanidine hydrochloride, guanidinoacetic acid, etc., and the organic acids are organic acids such as lactic acid, formic acid, and citric acid.
3. A method for preparing and detecting a fluorescent special paper for rapidly detecting Fe in the environment according to claim 1 3+ , characterized in that In step (1), the mass ratio of the guanidine salt / organic acid green solvent to dialdehyde cellulose is 20:1, the reaction temperature is 70 - 110 °C, and the reaction time is 1 - 3 h.
4. A method for preparing and detecting a fluorescent special paper for rapidly detecting Fe in the environment according to claim 1, characterized in that 3+ In step (2), the beating degree of the dissolving pulp is 40 - 80 °SR. 5. A method for preparing and detecting a fluorescent special paper for rapidly detecting Fe in the environment according to claim 1 3+ , characterized in that In step (2), the mass ratio of the dissolving pulp fibers to the cationic nanocellulose crystals is 1:1, 1:2, 1:3, 1:4, 1:5, and the reaction temperature is room temperature.
6. A method for preparing and detecting a fluorescent special paper for rapidly detecting Fe in the environment according to claim 1, characterized in that, 3+ In the step (4), Fe 3+ The solution concentration ranges from 10 to 100 μmol / L.
7. A method for preparing and detecting a fluorescent special paper for rapidly detecting Fe in the environment according to claim 1 3+ , characterized in that In step (4), Fe 3+ exists in the forms of FeCl3 and Fe2(SO4)3, etc.