CN113303976A - Identification for prompting excrement and application of identification on baby diaper - Google Patents

Identification for prompting excrement and application of identification on baby diaper Download PDF

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CN113303976A
CN113303976A CN202110215881.9A CN202110215881A CN113303976A CN 113303976 A CN113303976 A CN 113303976A CN 202110215881 A CN202110215881 A CN 202110215881A CN 113303976 A CN113303976 A CN 113303976A
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developing agent
minutes
urine
room temperature
stirring
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鲍佳
金利伟
鲍益平
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Hangzhou Coco Healthcare Products Co Ltd
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Hangzhou Coco Healthcare Products Co Ltd
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00Bandages or dressings; Absorbent pads
    • A61F13/15Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/42Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators with wetness indicator or alarm
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00Bandages or dressings; Absorbent pads
    • A61F13/15Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/45Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the shape
    • A61F13/49Absorbent articles specially adapted to be worn around the waist, e.g. diapers
    • A61F13/496Absorbent articles specially adapted to be worn around the waist, e.g. diapers in the form of pants or briefs

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  • Health & Medical Sciences (AREA)
  • Epidemiology (AREA)
  • Engineering & Computer Science (AREA)
  • Biomedical Technology (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Vascular Medicine (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
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Abstract

The invention relates to a material for detecting excrement and application thereof to a paper diaper. A marker for stool indication, wherein the color developing agent for the marker for stool indication has the following molecular formula: SrGdF5@CuBr2. This patent embodies baby's faecal sign through with the direct action of skatole in the excrement and urine, has higher degree of accuracy, has fine application prospect in baby diaper field.

Description

Identification for prompting excrement and application of identification on baby diaper
Technical Field
The invention relates to a material for detecting excrement and application thereof to a paper diaper.
Background
The paper diaper is a daily article for babies, is convenient to use and can also ensure the health of the babies, is mostly provided with a urine display line, and judges whether the paper diaper needs to be replaced or not through the change of the color of the paper diaper. The common urine display types mainly comprise a hot-melt urine display adhesive and an ink urine display adhesive, wherein the former utilizes substances in the urine display adhesive to generate color reaction to the change of pH value so as to enable the paper diaper to show color change, and the latter utilizes small molecular substances with color diluted by excrement so as to enable the color of a specific part of the paper diaper to disappear. [1-4] the two detection methods have large errors, such as the change of the environmental humidity and the scattered drinking water, etc., can cause the color change of the urine display material. Therefore, a more accurate detection method needs to be explored and applied to the production of novel diapers.
The human excrement yellow is formed by bile red derivatives of fecal bile pigment and urinary bile pigment, the odor is caused by products of bacterial action and mainly caused by indole, skatole, mercaptan and hydrosulfide, wherein the skatole is mainly present in the excrement, therefore, the material which develops color by the action of the skatole can be used as the excrement detection material with high accuracy, and the color developing agent is used without being matched with a specific instrument, so the cost is low, and the human excrement yellow detection material is easy to use [5-8 ]]. Through research and study on the literature, skatole is also called 3-Methylindole, which is called 3-Methylindole in English, and has a chemical formula of C9H9N, the molecular structure of which contains a plurality of-CH 3 bonds. The color developing agent is a color developing agent which directly shows the change of color through the reaction with substances, and the common color developing agent can not directly act with the skatole, so that the novel color developing agent which can act with the skatole is researched and developed, is applied to the paper diaper, and can be used for mainly checking excrement, thereby judging whether the paper diaper needs to be replaced.
Reference to the literature
[1]L.B.Rubia,R.Gomez,Journal of Pharmaceutical Sciences,1977,66,1656-1657.
[2]N.Ferronato,M.L.N.Pinedo,V.Torretta,Sustainability,2020,12,5055.
[3]Y.Budyk,A.Fullana,Journal of Environmental Chmical Engineering,2019,7,103341.
[4]S.C.Khoo,X.Y.Phang,C.M.Ng,K.L.Lim,S.S.Lam,N.L.Ma,Process Safety and Ennironmental Protection,2019,123,116-129.
[5]A.B.Patil,C.B.Zheng,L.Y.Ma,R.H.Wu,S.K.Mengane,Y.F.Zhang,X.T.Liu,Z.H. Meng,W.L.Zhang,Z.J.Xu,C.F.Chen,J.N.Huang,X.Y.Liu,Nanotechnology,2021,32, 065502.
[6]C.Y.Huang,H.C.Hsiao,Sensors,2020,20.
[7]C.Borghi,C.Bentivenga,E.R.Cosentino,International Journal of Cardiology,2020,320, 23-24.
[8]H.Y.Zhang,S.Liu,Journal of Alloys and Compounds,2020,842,155873。
Disclosure of Invention
In order to solve the above technical problems, the present application aims to provide a novel marker for stool indication, wherein when the color developing agent of the marker meets the stool, Br in the compound-Ions with multiple-CH's in skatole3Coordinated to form SrGdF5@ CuBr2-C9H9N complex, and the oleylamine has certain viscosity, so that the complex can be promoted to agglomerate, and Cu is shown2+The blue color of the ions, the brightness of which is in direct proportion to the skatole concentration, can be well applied to the quantitative detection of skatole. The excrement contains the skatole, so that the color developing agent can be used for detecting the excrement, the excrement detection is realized by utilizing the interaction of the color developing agent and specific components in the excrement, the accuracy is high, and the application prospect in the application field of the paper diaper is good.
In order to achieve the above object, the present application adopts the following technical solutions:
a marker for stool indication, wherein the color developing agent for the marker for stool indication has the following molecular formula: SrGdF5@CuBr2
Further, SrGdF5@CuBr2The surface of the color developing agent is coated with oleic acid
Further, the preparation method of the color developing agent for stool detection comprises the following steps:
1) dissolving (1-2) millimole of strontium acetate, and (1-2) millimole of gadolinium acetate and (2-4) millimole of ammonium fluoride in (4-8) milliliter of deionized water, and stirring at room temperature for 30-60 minutes, wherein the molar ratio of strontium acetate to ammonium fluoride is 1: 2;
2) adding 10-20 ml of oleylamine and 20-40 ml of octadecene into the mixture in the step 1), stirring the mixture at room temperature for 30-60 minutes, transferring the mixture into a hydrothermal kettle, and preserving the heat at the temperature of 170-190 ℃ for 16-20 hours;
3) centrifugally washing the product obtained in the step 2) for 3-5 times by using a mixed solution of cyclohexane and ethanol (the volume ratio is 1:3), and then dispersing the obtained nanocrystal in (4-8) ml of cyclohexane;
4) adding 1-2 ml of dilute hydrochloric acid (1.6 mol/L) into the solution obtained in the step 3), carrying out ultrasonic treatment in an ultrasonic cleaning instrument with the power of more than 1 kilowatt for 30-60 minutes, then carrying out centrifugal washing (1-2) times by using a mixed solution of ethanol and deionized water (the volume ratio is 1:3), and dispersing the obtained nanocrystals in (2-4) ml of deionized water;
5) stirring (30-60) mmol of copper acetate (0.5-1), 5-20 ml of glacial acetic acid and 40-60 ml of deionized water at room temperature for 30-60 min;
6) adding the nanocrystalline solution obtained in the step (4) into the solution obtained in the step (5), and stirring at room temperature for 30-60 minutes;
7) adding 0.5-1 mmol of ammonium bromide into the solution obtained in the step (6), and stirring at room temperature for 10-20 minutes;
8) adding 4-6 ml of oleylamine into the solution obtained in the step (7), stirring at room temperature for 30-60 minutes, then placing in an oven at 30-40 ℃ for standing for 24-48 hours, and finally storing the obtained color developing agent in a black bottle.
A baby diaper comprises a diaper body and a mark, wherein the mark is used for prompting excrement.
Further, the trousers body is also provided with urine development lines, and the molecular formula of the color developing agent material of the urine development lines is as follows: CaF2@Li0.1K0.9BiI4, CaF2@Li0.1K0.9BiI4The surface of the color developing agent is coated with polyacrylic acid, salicylic acid and EDTA. The molar ratio of polyacrylic acid, salicylic acid and EDTA is 1: 0.4-0.8: 0.1-0.3.
Further, after the color developing agent for excrement detection contacts excrement, the display mark is changed from light white to blue; the urine changes from light white to red after contacting with the urine, and the brightness of the red is proportional to the volume of the urine.
This patent adopts the solvothermal method to prepare out gadolinium strontium fluoride nanocrystalline to handle with hydrochloric acid and remove surface ligand, then use the nanocrystalline as the core, adopt room temperature stirring method to prepare out the colour-developing agent, then prepare out the colour-developing agent that is used for the sign of excrement and urine suggestion of oleyl amine ligand cladding through surface modification. After the skatole is added into the color developing agent, the solution is blue, the brightness degree of the solution is in a direct proportional relation with the skatole concentration, and the quantitative detection of the skatole can be well applied by fitting a relation curve of the blue light intensity and the skatole concentration. When the color developing agent is added into the feces of normal people, the feces can be obviously seen to be blue, and the brightness degree of the feces gradually deepens along with the increase of the volume of the feces. This patent embodies baby's faecal sign through with the direct action of skatole in the excrement and urine, has higher degree of accuracy, has fine application prospect in baby diaper field.
Drawings
The inductively coupled plasma atomic emission spectrometry analysis results of the color-developing agent identified in fig. 1.
FIG. 2 shows a Fourier-IR spectrum of the developer identified in FIG. 2.
Figure 3 shows the blue light intensity of the colour reagent plotted against skatole concentration.
FIG. 4 depicts blue light intensity versus stool quality for the color reagent identified.
FIG. 5 depicts blue light intensity versus urine volume for the color developer.
Figure 6 is a plot of blue light intensity versus skatole concentration for an identified color developer without oil amine ligand modification.
FIG. 7 shows the result of inductively coupled plasma atomic emission spectroscopy analysis of a urine chromogenic reagent.
FIG. 8 is a Fourier infrared transform spectrum of a urine line developing reagent.
FIG. 9 is a transmission electron micrograph of a urine line developing reagent.
FIG. 10 is a graph showing the relationship between the intensity of red light and the concentration of uric acid in a urinary line developer.
FIG. 11 is a graph of the red light intensity of the urine line developer versus the volume of urine.
FIG. 12 is a graph showing the relationship between the red light intensity and uric acid concentration of a urinary line-developing reagent without surface ligand modification.
FIG. 13 is a graph showing the relationship between the red light intensity and uric acid concentration of a polyacrylic acid ligand-alone modified urinary chromogenic line reagent.
FIG. 14 is a graph of red light intensity of a urinary development line color developing agent modified by a salicylic acid ligand alone as a function of uric acid concentration.
FIG. 15 is a graph of the relationship between the red light intensity and uric acid concentration of an EDTA ligand-modified urinary line-developing color-developing agent alone.
Detailed Description
Experimental part main reagents: potassium acetate (99.0%), lithium acetate (99.0%), calcium acetate (99.0%), bismuth subnitrate (98%), lutetium acetate (99.9%), potassium iodide (99.0%), glacial acetic acid (100%), oleic acid, octadecene (90%), strontium acetate (99.0%), gadolinium acetate (99.9%), ammonium fluoride (99.0%), copper acetate (99.9%), glacial acetic acid (100%), oleylamine; polyacrylic acid (99%), uric acid (99%), ammonium bromide and skatole were purchased from Sigma-Aldrich, cyclohexane, ethanol, diluted hydrochloric acid and deionized water were purchased from national drug group chemical agents limited, and test feces and urine were taken from normal infants.
SrGdF5@CuBr2Preparation of
Dissolving 1 mmol of strontium acetate, 1 mmol of gadolinium acetate and 2 mmol of ammonium fluoride in 4 ml of deionized water, and stirring at room temperature for 30 minutes; then adding 20 ml of oleylamine and 10 ml of octadecene, stirring for 60 minutes at room temperature, then transferring to a hydrothermal kettle, and preserving heat at 180 ℃ for 12 hours; mixing SrGdF5Centrifugally washing with a mixture of cyclohexane and ethanol (volume ratio of 1:3) for 3 times, and then adding SrGdF5The nanocrystals were dispersed in 4 ml of cyclohexane; adding 1 ml of dilute hydrochloric acid into the solution, carrying out ultrasonic treatment in an ultrasonic cleaning instrument with the power of 1 kilowatt for 30 minutes, then carrying out centrifugal washing for 1 time by using a mixed solution of ethanol and deionized water (the volume ratio is 1:3), and carrying out SrGdF treatment5Dispersing the nanocrystals in 2 ml of deionized water; stirring 1 mmol of copper acetate, 10 ml of glacial acetic acid and 40 ml of deionized water at room temperature for 30 minutes to obtain a solution A; adding SrGdF into the solution A5Stirring the nanocrystalline solution at room temperature for 60 minutes; then, 0.5 mmol of ammonium bromide is added into the solution, and the solution is stirred for 10 minutes at room temperature; subsequently, 8 ml of oleylamine was added, stirred at room temperature for 30 minutes, and then placed in an oven at 30 ℃ for 24 hours, and finally the resultant color developing agent was stored in a black bottle.
Characterization apparatus and method
Inductively coupled plasma atomic emission spectroscopy (ZX-Z5000-WLD5000, powder sample, frequency 50/60Hz), Fourier Infrared transform spectroscopy (Nicolet 380), Transmission Electron microscopy (TEM, FEI Tecnai G2F 20), Spectroscopy (FLUROUB-B, HORISR JOBIN YVON).
Preparation of atomic emission spectrometry test sample: freezing and drying the color developing agent to obtain a powdery sample;
preparation of Fourier infrared transform spectrum sample: the tablet is prepared by a superior pure KBr tablet method;
preparation of transmission electron microscope samples: dissolving a little developer in 4 ml of ethanol solution, and dropping 3-6 drops of liquid on the ultrathin carbon film after ultrasonic treatment for 5 minutes.
The method for detecting skatole comprises the following steps: and (3) removing a certain volume of color developing agent, dividing the color developing agent into a plurality of groups, adding skatole with different molar quantities into each group, representing the change of the fluorescence intensity of the skatole by a fluorescence spectrometer, and fitting a standard curve.
The concentration of skatole refers to the skatole content per unit volume of aqueous solution, and the volume of feces refers to the total volume of feces.
As shown in FIG. 1, the result of atomic emission spectroscopy analysis of inductively coupled plasma shows that the oleylamine ligand modified gadolinium strontium fluoride-copper bromide product contains Sr, Gd, F, Cu and Br elements, the molar percentages of which are respectively 10.77%, 11.03%, 48.56%, 9.12% and 20.52%, and are substantially consistent with the molar percentage added in the raw material, which indicates that the obtained product is SrGdF5@CuBr2. As shown in fig. 2, the fourier transform infrared spectroscopy test results indicated that the surface of the product contained oleylamine ligand. The preparation process of the product comprises the following steps: firstly, strontium ions in the raw material are combined with fluoride ions to form oleylamine-coated SrGdF5Removing surface ligand by hydrochloric acid treatment, and then treating with SrGdF5Copper bromide is formed on the surface, and the oleylamine ligand is further coated by surface modification.
The product of gadolinium strontium fluoride-copper bromide modified by oleylamine ligand is light white, and the color of the product is changed into blue after a small amount of skatole is added into the color developing agent. The mechanism is explained as follows: br in the Complex-Ions with multiple-CH's in skatole3Coordinate to form SrGdF5@CuBr2-C9H9N complex, and the oleylamine has certain viscosity, so that the complex can be promoted to agglomerate, and Cu is shown2+The blue color of the ion. With the increase of the skatole concentration, the agglomeration degree of the complex compound is increased, the color of the solution is gradually deepened, and the change amplitude can be characterized by fluorescence spectrum. As shown in fig. 3, with the increasing of skatole concentration, the intensity of blue light is gradually enhanced, and a clear positive correlation is shown, and the standard curve can be used for quantitative determination of skatole. To further demonstrate its utility, a test was performed on normal infant feces.
As shown in figure 4, after a small amount of stool sample is added into the oleylamine ligand modified gadolinium strontium fluoride-copper bromide color-developing agent, the color-developing agent is blue, the color of the color-developing agent is gradually deepened along with the further increase of the stool quality, the change trend of the color-developing agent is positively correlated with the stool quality, and the color-developing agent can be used for detecting the stool as a standard curve. The color developing agent provided by the invention is used for manufacturing the paper diaper, can intuitively judge whether the paper diaper needs to be replaced or not according to the change of the color, and has good application prospect.
In order to verify the accuracy of the oleylamine ligand modified gadolinium strontium fluoride-copper bromide on the detection of the feces, the relation between the blue light intensity and the urine volume is researched. As shown in FIG. 5, no color change occurred with the addition of urine to this reagent, even when the volume of urine was increased to 10 ml, indicating that this reagent has a high accuracy for stool examination.
In order to verify the importance of adopting oleylamine ligand to modify gadolinium strontium fluoride-copper bromide, a ligand-free modified gadolinium strontium fluoride-copper bromide color developing agent is prepared. As shown in fig. 6, when skatole was added to this developer, no color change occurred, and even when the amount of skatole was increased to 1 μmol/l, no color change occurred in the developer, indicating that the surface ligands contributed to the promotion of complex aggregation.
10 identical marks for stool indication were made with a small amount of developer, and 40 g of extracted 10 normal infant stools were added to the marks, respectively, with the blue intensity varying approximately between 600 and 650, as shown in Table 1. Furthermore, the change rule of the color intensity of the color developing agent can be adjusted by changing the concentration of the color developing agent on the mark, so that different types of paper diapers can be manufactured more flexibly according to different requirements.
Figure RE-GDA0003149243580000051
TABLE 1
CaF2@Li0.1K0.9BiI4Preparation of
Dissolving 1 mmol of calcium acetate and 2 mmol of ammonium fluoride in 4 ml of deionized water, and stirring at room temperature for 30 minutes; then adding 20 ml of oleic acid and 10 ml of octadecene, stirring for 60 minutes at room temperature, then transferring to a hydrothermal kettle, and preserving heat at 180 ℃ for 12 hours; mixing CaF2Centrifugally washing with a mixture of cyclohexane and ethanol (volume ratio of 1:3) for 3 times, and then adding CaF2The nanocrystals were dispersed in 4 ml of cyclohexane; adding 1 ml of dilute hydrochloric acid into the solution, carrying out ultrasonic treatment in an ultrasonic cleaning instrument with the power of 1 kilowatt for 30 minutes, then carrying out centrifugal washing for 1 time by using a mixed solution of ethanol and deionized water (the volume ratio is 1:3), and obtaining CaF2Dispersing the nanocrystals in 2 ml of deionized water; stirring 1 mmol of basic bismuth nitrate, 0.9 mmol of potassium acetate, 0.1 mmol of lithium acetate, 10 ml of glacial acetic acid and 40 ml of deionized water at room temperature for 30 minutes to obtain a solution A; adding CaF into the solution A2Stirring the nanocrystalline solution at room temperature for 60 minutes; then, 0.8 mmol of potassium iodide and 0.3 ml of dilute hydrochloric acid were added to the above solution, and the mixture was stirred at room temperature for 10 minutes; polyacrylic acid, salicylic acid and EDTA (in a molar ratio of 1:0.6: 0.2) were then added, the total molar amount of which was 0.8 mmol), stirred at room temperature for 5 minutes, then placed in an oven at 30 ℃ for 24 hours, and the resulting developer was finally stored in a black bottle.
Characterization apparatus and method
Inductively coupled plasma atomic emission spectroscopy (ZX-Z5000-WLD5000, powder sample, frequency 50/60Hz), Fourier Infrared transform spectroscopy (Nicolet 380), Transmission Electron microscopy (TEM, FEI Tecnai G2F 20), Spectroscopy (FLUROUB-B, HORIBA JOBIN YVON).
Preparation of atomic emission spectrometry test sample: freezing and drying the color developing agent to obtain a powdery sample;
preparation of Fourier infrared transform spectrum sample: the tablet is prepared by a superior pure KBr tablet method;
preparation of transmission electron microscope samples: dissolving a little developer in 4 ml of ethanol solution, and dropping 3-6 drops of liquid on the ultrathin carbon film after ultrasonic treatment for 5 minutes.
The detection method of uric acid comprises the following steps: removing color developing agents with certain volume, dividing the color developing agents into a plurality of groups, adding different molar amounts of uric acid into each group, representing the change of the fluorescence intensity by a fluorescence spectrometer, and fitting a standard curve.
The concentration of uric acid refers to the content of uric acid in a unit volume of aqueous solution, and the volume of urine refers to the total volume of urine.
Data analysis and discussion
As shown in FIG. 7, the result of atomic emission spectroscopy analysis of inductively coupled plasma indicates that the product of calcium fluoride-bismuth potassium iodide modified by three ligands of polyacrylic acid, salicylic acid and EDTA contains Ca, Li, K, Bi, I and F elements, the molar percentages of which are respectively 11.32%, 1.02%, 9.36%, 10.13%, 45.13% and 23.04%, and are substantially the same as the molar percentage added in the raw material, which indicates that the obtained product is CaF2@Li0.1K0.9BiI4. As shown in fig. 8, the fourier transform infrared spectroscopy test result indicates that the surface of the product contains carboxyl functional groups derived from polyacrylic acid, salicylic acid and EDTA ligands. The analysis result of the transmission electron microscope shows that the product has irregular appearance. The preparation process of the product comprises the following steps: firstly, calcium ions in raw materials are combined with fluoride ions to form CaF coated with oleic acid2Removing surface ligand by hydrochloric acid treatment, and then treating in CaF2Bismuth potassium lithium iodide is formed on the surface, and polyacrylic acid, salicylic acid and EDTA ligand are coated by further surface modification.
Polyacrylic acid, salicylic acid and EDTA three-ligand modified calcium fluoride-potassium bismuth iodide product is light white in colorAfter adding a small amount of uric acid, the color turned red. The mechanism is explained as follows: carboxyl in the ligand and-NH bond in uric acid promote lithium bismuth potassium iodide and uric acid to form a complex through electrostatic attraction, the complex is red finally, the concentration of the complex is increased along with the increase of the amount of uric acid, the color of the solution is gradually deepened, and the change amplitude can be characterized through fluorescence spectrum. As shown in FIG. 10, the intensity of red light is gradually enhanced with the continuous increase of uric acid concentration, and a clear positive correlation is shown, so that the standard curve can be used for quantitative detection of uric acid. In addition, when the urine volume reaches a certain content, EDTA adsorbs excessive Na+Ions and positively charged sodium ions can adsorb negatively charged chloride ions in urine, and the chloride ions are partially exchanged with iodine ions in the bismuth potassium lithium iodide to cause a color developing agent for urine line development to be changed into red.
As shown in fig. 11, after a small amount of urine sample is added into the polyacrylic acid, salicylic acid and EDTA three-ligand modified color-developing agent, the color-developing agent becomes red, the color of the color-developing agent gradually deepens with the further increase of the urine volume, the change trend of the color-developing agent is in positive correlation with the urine volume, and the color-developing agent can be used for urine detection as a standard curve. The color developing agent provided by the invention is used for manufacturing the paper diaper, can intuitively judge whether the paper diaper needs to be replaced or not according to the change of the color, and has good application prospect. In addition, when the urine reaches a certain critical volume, EDTA adsorbs excessive Na+Ions and positively charged sodium ions can adsorb negatively charged chloride ions in urine, and the chloride ions are partially exchanged with iodine ions in the bismuth potassium lithium iodide, so that a color developing agent for developing the urine line is changed into red, and at the moment, the paper diaper has to be replaced.
In order to verify the importance of adopting polyacrylic acid, salicylic acid and EDTA three ligands to modify calcium fluoride-lithium bismuth potassium iodide, a ligand-free modified color-developing agent is prepared. As shown in fig. 12, no color change occurred with the addition of uric acid to this developer, and even when the amount of uric acid was increased to 1 micromole/liter, no color change occurred in the developer, indicating that the surface ligand helps to promote the binding of the developer and uric acid by surface action to form a complex. The adoption of the three-ligand modified color developing agent is an important innovation point of the invention.
In order to verify the effect of each ligand, polyacrylic acid, salicylic acid or EDTA mono-ligand modified calcium fluoride-lithium bismuth potassium iodide compound is prepared respectively. As shown in fig. 13 and 14, when uric acid is added to the polyacrylic acid or salicylic acid ligand-modified calcium fluoride-bismuth potassium lithium iodide color developing agent alone, the increase of the intensity of red light is very small, and no color change occurs. This indicates that the dual ligands generate obvious synergistic effect, promote the formation of the complex by co-adsorbing uric acid, and result in significant change of luminous intensity.
As shown in FIG. 15, the luminescence intensity of the EDTA single-ligand modified calcium fluoride-lithium bismuth potassium iodide developer hardly changes with the change of uric acid concentration, and when excessive Cl is added into the solution-After ionization, the developer turns red, indicating Cl-The ions can partially exchange with the iodide ions, thereby changing the color of the developer.
In order to research the influence of different proportions of polyacrylic acid, salicylic acid and EDTA on the surface of the calcium fluoride-bismuth potassium lithium iodide color developing agent on urine detection, compounds with different surface ligand proportions are prepared, and comprise 1:0.4:0.2, 1:0.5:0.2, 1:0.6:0.2, 1:0.7:0.2, 1:0.8:0.2, 1:0.6:0.1 and 1:0.6: 0.3. As shown in Table 2, 0.5X 10 was added to an equal volume (5 ml) of developer-3Millimole of uric acid, when the ratio is 1:0.6:0.2, the change of the red light intensity before and after addition of uric acid is the largest, about 2.5 times.
TABLE 2
Polyacrylic acid: salicylic acid: EDTA Change of red light intensity before and after addition of uric acid
1:0.4:0.2 1.6
1:0.5:0.2 1.9
1:0.6:0.2 2.5
1:0.7:0.2 2.3
1:0.8:0.2 2.1
1:0.6:0.1 2.4
1:0.6:0.3 2.3
The length of a urine display line of a common baby diaper is 200MM, and the change of the diaper is judged according to the color change or fading position of the urine display line, but the color depth change is not obvious. The urine display line provided by the invention has the advantages that the color depth change of the urine display line is very obvious, and whether the paper diaper needs to be replaced or not is judged intuitively and accurately according to the color depth. 10 identical urine development lines were prepared with a very small amount of color developing agent, and 20 ml of the extracted urine of 10 normal infants was dropped on the urine development lines, respectively, and the change of the intensity of red color was approximately between 5000-. Furthermore, the change rule of the color intensity of the color developing agent can be adjusted by changing the concentration of the color developing agent on the urine development line, different types of paper diapers can be manufactured more flexibly according to different requirements, and in addition, when the color developing agent is changed into red, the paper diapers are prompted to be replaced.
Figure RE-GDA0003149243580000081
TABLE 3
This patent adopts the solvothermal method to prepare out gadolinium strontium fluoride nanocrystalline to handle with hydrochloric acid and remove surface ligand, then use the nanocrystalline as the core, adopt room temperature stirring method to prepare out the colour-developing agent, then prepare out the colour-developing agent that is used for the sign of excrement and urine suggestion of gadolinium strontium fluoride-cupric bromide of oleyl amine ligand cladding through surface modification. After the skatole is added into the color developing agent, the solution is dark blue, the brightness degree of the solution is in a direct proportional relation with the skatole concentration, and the quantitative detection of the skatole can be well applied by fitting a relation curve of the blue light intensity and the skatole concentration. On the basis, the feces of normal people are added into the gadolinium strontium fluoride-copper bromide color developing agent, so that blue color can be obviously seen, and the brightness degree of the feces is gradually deepened along with the increase of the quality of the feces. Compared with the traditional pH detection method, the color developing agent which reflects the quality of the infant feces through the direct action of the color developing agent and the feces components has higher accuracy and has good application prospect in the field of infant diapers. Preparing calcium fluoride nanocrystalline by adopting a solvothermal method, removing a surface ligand by using hydrochloric acid treatment, preparing a calcium fluoride-bismuth potassium lithium iodide compound color developing agent by taking the nanocrystalline as a core and adopting a room-temperature stirring method, and preparing the calcium fluoride-bismuth potassium lithium iodide compound color developing agent coated by polyacrylic acid, salicylic acid and EDTA through surface modification. When the color developing agent is added with uric acid, the solution is dark red, the brightness degree of the solution is in direct proportion to the concentration of the uric acid, and the quantitative detection of the uric acid can be well applied by fitting a relation curve of the intensity of red light and the concentration of the uric acid. On the basis, normal human urine is added into the calcium fluoride-bismuth potassium lithium iodide color developing agent, the color can be obviously seen, the brightness degree of the color is gradually deepened along with the increase of the urine volume, and after the urine volume reaches a certain degree, because EDTA adsorbs excessive Na+The ions, positively charged sodium ions can adsorb negatively charged chloride ions in urine, and the chloride ions are partially exchanged with iodine ions in the lithium bismuth potassium iodide, so that the color developing agent is converted into the color developing agentRed, indicating that the diaper must be replaced. Compared with the traditional pH detection method, the color developing agent which reflects the volume of the baby urine through the direct action of the color developing agent and urine components has higher accuracy and has good application prospect in the field of baby diapers.
The baby diaper of this patent shows the sign of line and being used for excrement and urine suggestion including the trousers body and the urine thereon, and the sign is in trousers body crotch portion region, and the sign can be circular, square or other cartoon figure, can show the line in order to be distinguished from traditional straight strip type urine, can accurately judge whether have excrement and urine to discharge through observing the sign, judges more accurately through the sense of smell for traditional. The urine display line made of the materials is straight, is mainly positioned in the crotch area of the trousers body, a small part of the urine display line extends to the front waist area and the rear waist area, and the length of the urine display line is not more than 100 MM. Most of urine on the paper diaper is concentrated on the crotch area of the paper diaper, and especially when a user is in a standing state, most of urine near the front and rear waist areas above the crotch of the paper diaper also falls downwards into the crotch area, so that when the urine in the crotch area is pure too much, even if the urine near the front and rear waist areas above the crotch of the paper diaper is not much or not enough, the user can feel uncomfortable. Under this condition, traditional urine shows line because the urine of panty-shape diapers crotch portion top near back waist region shows the line and does not appear the suggestion, and the nurse personnel can't in time change, and uses the panty-shape diapers of this patent, only needs to observe the colour degree of depth that crotch portion regional urine shows the line and can judge the storage condition of urine, and then makes the accurate judgement whether change panty-shape diapers. The urine of this patent shows line and uses on being particularly suitable for baby's pull-up diaper.

Claims (8)

1. The mark for the stool prompt is characterized in that a color developing agent for the mark for the stool prompt has the following molecular formula: SrGdF5@CuBr2
2. Color developer for stool examination according to claim 1, characterized in that SrGdF5@CuBr2The surface of the color developing agent is coated with oleic acid.
3. The method for preparing a color-developing agent for stool examination according to claim 2, comprising the steps of:
1) dissolving (1-2) millimole of strontium acetate, and (1-2) millimole of gadolinium acetate and (2-4) millimole of ammonium fluoride in (4-8) milliliter of deionized water, and stirring at room temperature for 30-60 minutes, wherein the molar ratio of strontium acetate to ammonium fluoride is 1: 2;
2) adding 10-20 ml of oleylamine and 20-40 ml of octadecene into 1), stirring at room temperature for 30-60 min, transferring to a hydrothermal kettle, and adding at 170%oC-190oC, preserving heat for 16-20 hours;
3) centrifugally washing the product obtained in the step 2) for 3-5 times by using a mixed solution of cyclohexane and ethanol (the volume ratio is 1:3), and then dispersing the obtained nanocrystal in (4-8) ml of cyclohexane;
4) adding 1-2 ml of dilute hydrochloric acid (1.6 mol/L) into the solution obtained in the step 3), carrying out ultrasonic treatment in an ultrasonic cleaning instrument with the power of more than 1 kilowatt for 30-60 minutes, then carrying out centrifugal washing (1-2) times by using a mixed solution of ethanol and deionized water (the volume ratio is 1:3), and dispersing the obtained nanocrystals in (2-4) ml of deionized water;
5) stirring (30-60) mmol of copper acetate (0.5-1), 5-20 ml of glacial acetic acid and 40-60 ml of deionized water at room temperature for 30-60 min;
6) adding the nanocrystalline solution obtained in the step (4) into the solution obtained in the step (5), and stirring at room temperature for 30-60 minutes;
7) adding 0.5-1 mmol of ammonium bromide into the solution obtained in the step (6), and stirring at room temperature for 10-20 minutes;
8) adding 4-6 ml of oleylamine into the solution obtained in the step (7), stirring at room temperature for 30-60 minutes, and then placing the mixture in a place of 30-40 minutesoAnd C, standing in an oven for 24-48 hours, and finally storing the obtained color developing agent in a black bottle.
4. A baby diaper comprising a diaper body and a mark, the mark being as defined in claim 1 for a stool cue.
5. The baby diaper according to claim 4, wherein the diaper body is further provided with a urine development line, and the formula of the color developing agent material of the urine development line is as follows: CaF2@Li0.1K0.9BiI4,CaF2@Li0.1K0.9BiI4The surface of the color developing agent is coated with polyacrylic acid, salicylic acid and EDTA.
6. An infant diaper according to claim 5, wherein the molar ratio of polyacrylic acid, salicylic acid and EDTA is 1: 0.4-0.8: 0.1-0.3.
7. The baby diaper according to claim 5, wherein the method for preparing the urine revealing line comprises the following steps:
1) dissolving (1-2) millimole of calcium acetate and (2-4) millimole of ammonium fluoride in (4-8) ml of deionized water, and stirring at room temperature for 30-60 minutes, wherein the molar ratio of the calcium acetate to the ammonium fluoride is 1: 2;
2) adding (20-30) ml of oleic acid and (10-20) ml of octadecene into the mixture in the step 1), stirring the mixture at room temperature for (30-60) minutes, transferring the mixture into a hydrothermal kettle, and performing hydrothermal reaction at 160 DEGoC-200oC, preserving heat for 12-24 hours;
3) centrifugally washing the product obtained in the step 2) for 3-5 times by using a mixed solution of cyclohexane and ethanol (the volume ratio is 1:3), and then dispersing the obtained nanocrystal in (4-8) ml of cyclohexane;
4) adding 1-2 ml of dilute hydrochloric acid (1.6 mol/L) into the solution obtained in the step 3), carrying out ultrasonic treatment in an ultrasonic cleaning instrument with the power of more than 1 kilowatt for 30-60 minutes, then carrying out centrifugal washing (1-2) times by using a mixed solution of ethanol and deionized water (the volume ratio is 1:3), and dispersing the obtained nanocrystals in (2-4) ml of deionized water;
5) stirring (30-60) millimoles of basic bismuth nitrate (0.5-1), potassium acetate, lithium acetate and glacial acetic acid (5-20) ml and deionized water (40-60) ml at room temperature for 30-60 minutes, wherein the molar ratio of the potassium acetate to the lithium acetate is 9:1, and the total molar weight of the potassium acetate to the lithium acetate is the same as that of the bismuth nitrate;
6) adding the nanocrystalline solution obtained in the step (4) into the solution obtained in the step (5), and stirring at room temperature for 30-60 minutes;
7) adding potassium iodide (4/5 molar weight of bismuth nitrate) and dilute hydrochloric acid (0.3-1 ml) into the solution obtained in the step (6), and stirring at room temperature for 10-20 minutes;
8) adding polyacrylic acid, salicylic acid and EDTA (the molar ratio is 1: (0.4-0.8): (0.1-0.3) the total molar amount of which is the same as that of potassium iodide), stirring at room temperature for 2-5 minutes, and then placing at 30-40oAnd C, standing in an oven for 24-48 hours, and finally storing the obtained color developing agent in a black bottle.
8. The baby diaper according to claim 5, wherein the color developing agent for feces detection shows a shift of the mark from pale white to blue after contacting feces; the urine changes from light white to red after contacting with the urine, and the brightness of the red is proportional to the volume of the urine.
CN202110215881.9A 2021-02-26 2021-02-26 Identification for prompting excrement and application of identification on baby diaper Pending CN113303976A (en)

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Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
刘捷、徐嵩、李兰敏、徐世平: "3-甲基吲哚溴代中的异常现象", 《合成化学》 *
赵克键: "《现代药学名词手册》", 31 October 2004 *

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Application publication date: 20210827