CN112666141B - Fluorescent ratio detection method for phosphorus-killing pesticide - Google Patents
Fluorescent ratio detection method for phosphorus-killing pesticide Download PDFInfo
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- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention discloses a nitrogen-doped fluorescent carbon quantum dot which is synthesized by taking natural high molecular saccharides as a carbon source, adding the nitrogen source and adopting a one-step hydrothermal method. Because of the dual excitation-single emission fluorescence characteristic of the nitrogen-doped fluorescent carbon quantum dots, the single nitrogen-doped fluorescent carbon quantum dots are used as fluorophores, no fluorophores are needed to be added, dual output signals can be realized, and a fluorescence ratio sensor is built. Accordingly, a fluorescence ratio detection method of the phosphorus-volt pesticide is established. With the addition of the phosphorus, the nitrogen-doped fluorescent carbon quantum dot can react within 1min, the excitation peak at 235nm is quenched continuously, and the fluorescent peak at 327nm is kept unchanged basically, and a standard curve is established according to the excitation peak; and detecting the phosphorus volt-killing in the sample based on the standard curve. In a word, the method does not need expensive large instruments, is simple to operate, is environment-friendly and quick in response, and has potential application value in the real-time detection of the phosphorus volt.
Description
Technical Field
The invention belongs to the technical field of pesticide analysis and detection, and particularly relates to a fluorescence ratio detection method of a phosphorus-killing pesticide.
Background
The organophosphorus pesticides are organic compound pesticides containing phosphate or thiophosphate pesticides, and are mainly used for preventing and controlling plant diseases and insect pests. Due to the advantages of relatively rapid environmental degradation speed, high efficiency, safety to plants, low price and the like, the organic chlorine pesticide has been widely replaced and is widely popularized worldwide from the fifth sixty of 20 th century. The organophosphorus insecticide is a broad-spectrum high-efficiency organophosphorus insecticide and mite-removing agent, and can be extensively used for preventing and controlling plant diseases and insect pests in grain, fruit tree, vegetable and cotton. Once inside the body, the virucide can bind and thus inhibit acetylcholinesterase activity, impeding the catalytic hydrolysis of thioacetylcholine, causing neurotoxicity. Therefore, it is a highly toxic neurotoxin which can cause damage to human body functions even at low concentrations, can put the person into toxic states such as vomiting, cold sweat, mental abnormality, and can cause respiratory paralysis and even death in severe cases. The residue of phosphorus in crops and the environment also poses a significant hazard to mammals and the environment: it can enter from the digestive tract and respiratory tract through the polluted water body and through the food chain to endanger human body.
Currently, chromatography is still the mainstream method of detection of phosphorus by volt, including high performance liquid chromatography, gas chromatography-mass spectrometry technology, liquid chromatography-mass spectrometry technology, ultra-high performance liquid chromatography-mass spectrometry/mass spectrometry technology and the like. The chromatographic or/and the combined technology can realize high-flux detection of the phosphorus-volt and other organophosphorus pesticides, but the equipment is expensive, the operation is complex, the analysis time is long, the requirement on operators is high, and the real-time detection of emergency events is not facilitated. Therefore, the development of simple, rapid and cheap technology for detecting the phosphorus volt-age has important significance.
The fluorescence detection technology can rapidly respond to the target detection object with high sensitivity, is simple to operate and low in cost, and has been paid attention to by more and more students. However, most of the common analytical detection techniques focus on the detection of a single signal, which is easily interfered by background signals, instrument noise and surrounding environment, and reduces the accuracy thereof. In order to overcome the defects, the ratio type fluorescence sensor takes the ratio of two fluorescence signals as an output signal, which is equivalent to introducing an internal standard for the sensor, can effectively eliminate the systematic error and improve the accuracy. In order to obtain multiple fluorescent signals, a common strategy is to introduce different fluorophores, but adding fluorophores not only increases the operation steps and detection costs, but also may interfere or repel the target detector. Thus, a fluorophore with multiple fluorescent signals would be more advantageous in the construction of a ratio-type sensor. Although the construction of ratio sensors based on a single fluorophore with dual emission properties has also been reported, most reported fluorescence sensors have focused on the emission spectrum, and few fluorescence sensors based on the excitation spectrum, let alone ratio fluorescence sensors based on the excitation spectrum, have been reported. For innovative scientific researches, a quicker and wider channel is provided for the material detection technology in later life.
Disclosure of Invention
The invention aims to provide a fluorescent ratio detection method of a green and quick volt-phosphate pesticide with low cost.
In order to solve the technical problems, the invention adopts the following technical scheme:
the nitrogen doped fluorescent carbon quantum dot is synthesized by taking natural high molecular saccharides as a carbon source, adding a nitrogen source and adopting a one-step hydrothermal method; the nitrogen doped fluorescent carbon quantum dot has the characteristic of double excitation and single emission, and when the fixed emission wavelength is 400-440 nm, the nitrogen doped fluorescent carbon quantum dot has an excitation peak at about 235nm and 327nm respectively.
The natural high molecular sugar is one or more of cellulose, xylose and cellobiose; the nitrogen source is one or more of urea, ammonium bicarbonate, dicyandiamide, ethylenediamine and ammonia water.
According to the preparation method of the nitrogen-doped fluorescent carbon quantum dot, natural high molecular saccharides are used as a carbon source, the nitrogen source is added, deionized water is added into a hydrothermal reaction kettle, hydrothermal reaction is carried out in a high-temperature environment, and a nitrogen-doped fluorescent carbon quantum dot crude product is obtained through cooling; and filtering the crude product by a filter membrane, and dialyzing by a dialysis bag to obtain a nitrogen doped fluorescent carbon quantum dot purified product.
The natural high molecular sugar is 0.05-0.5 g, nitrogen source is 0.2-2.0 g, deionized water is 10-50 mL, hydrothermal reaction is carried out for 1-15 h at 140-210 ℃, and dialysis is carried out for 12-36 h by using a dialysis bag with 500-1000 Da.
The natural high molecular sugar is 0.2g of cellobiose, the nitrogen source is 0.75g of urea, the deionized water is 20mL, the hydrothermal reaction is carried out for 4h at 180 ℃, the dialysis is carried out for 24h by adopting a dialysis bag of 1000Da, and the volume of the solution after dialysis is fixed to 50mL.
The nitrogen-doped fluorescent carbon quantum dot is used for visual detection of phosphorus and preparation of a ratio-type fluorescent sensor.
According to the fluorescence ratio detection method of the phosphorus-killing pesticide, the nitrogen-doped fluorescent carbon quantum dot and the phosphorus-killing standard substance are used for preparing a phosphorus-killing solution with gradient concentration, the emission wavelength is fixed at 400-440 nm, a fluorescence excitation spectrum is scanned by a fluorescence spectrophotometer, and an excitation peak 235nm (I 1 ) And 327nm (I) 2 ) Is calculated by the ratio I of fluorescence excitation peak intensities 2 /I 1 Establishing a standard curve by taking the phosphorus killing concentration as an abscissa and taking the phosphorus killing concentration as an ordinate; and detecting the phosphorus volt-killing in the sample based on the standard curve.
The emission wavelength is fixed at 420-430 nm.
The mixed solution of methanol and water is used as a solvent, and the ratio of the methanol to the water in the mixed solution of the methanol and the water is 1-4:4-1.
The ratio of methanol to water in the mixed solution of methanol and water is 1:4, 2:3, 3:2 or 4:1.
Aiming at the problem that the existing phosphorus killing lacks effective targeted detection measures, the inventor develops a nitrogen-doped fluorescent carbon quantum dot, takes natural high molecular saccharides as a carbon source, adds a nitrogen source, and synthesizes the nitrogen-doped fluorescent carbon quantum dot by adopting a one-step hydrothermal method; the nitrogen-doped fluorescent carbon quantum dot has the characteristic of double excitation and single emission, and when the fixed emission wavelength is 400-440 nm, the nitrogen-doped fluorescent carbon quantum dot has an excitation peak at 235nm and 327nm respectively. Because of the dual excitation-single emission fluorescence characteristic of the nitrogen-doped fluorescent carbon quantum dots, the single nitrogen-doped fluorescent carbon quantum dots are used as fluorophores, no fluorophores are needed to be added, dual output signals can be realized, and a fluorescence ratio sensor is built. Accordingly, the inventors established a fluorescence ratio detection method for the phosphorus-volt pesticide. With the addition of the phosphorus, the nitrogen-doped fluorescent carbon quantum dot can react within 1min, the excitation peak at 235nm is quenched continuously, and the fluorescent peak at 327nm is kept unchanged basically, and a standard curve is established according to the excitation peak; and detecting the phosphorus volt-killing in the sample based on the standard curve. In a word, the method does not need expensive large instruments, is simple to operate, is environment-friendly and quick in response, and has potential application value in the real-time detection of the phosphorus volt.
Compared with the prior art, the invention has at least the following advantages:
(1) The nitrogen-doped fluorescent carbon quantum dot uses natural high molecular saccharides as carbon sources, and has wide sources, low cost and easy obtainment.
(2) The nitrogen-doped fluorescent carbon quantum dot has the fluorescent characteristic of double excitation and single emission, and can provide two fluorescent signals without adding other fluorophores; most of the existing fluorescent sensors are based on emission spectra, and the invention creatively utilizes the excitation spectra to construct the ratio-type fluorescent sensor for the phosphorus volt, and identifies the ratio-type fluorescent sensor based on the response of the fluorescence excitation spectra to the phosphorus volt, thereby providing a new idea for constructing the ratio-type fluorescent sensor, and being green and environment-friendly and low in cost.
(3) The invention adopts the ratio-type fluorescent sensor to carry out the detection of the phosphorus and has the characteristics of high accuracy, good sensitivity, quick response and the like.
(4) The invention has good application prospect and application value in the field of analysis and detection, and can be applied to detection of the phosphorus volt-killing in environmental water samples and agricultural products.
Drawings
Fig. 1 is a Transmission Electron Microscope (TEM) image of fluorescent carbon quantum dots.
Fig. 2 is a graph of excitation and emission spectra of fluorescent carbon quantum dots.
FIG. 3 is a graph of fluorescence excitation spectra at 235nm and 327nm of different concentrations of Fungicide versus fluorescent carbon quantum dots versus different concentrations of Fungicide.
Fig. 4 is a standard graph for detecting phosphorus on a volt.
FIG. 5 is a graph of fluorescence of nitrogen-doped fluorescent carbon quantum dots under 254nm ultraviolet radiation in the presence of different concentrations of Fungicide, wherein: 1-11 corresponds to a phosphorus killing concentration of 0.00,0.16,0.24,0.40,0.60,0.80,1.00,2.00,4.00,6.00,10.00 μg/mL, respectively.
Fig. 6 is a graph of the fluorescence ratio response of nitrogen-doped fluorescent carbon quantum dots to virucide and other interfering substances.
Detailed Description
Example 1 preparation of Nitrogen-doped fluorescent carbon Quantum dots
Adding 0.2g of cellobiose, 0.75g of urea and 20mL of deionized water into a hydrothermal reaction kettle, reacting for 4 hours at 180 ℃, and cooling to room temperature to obtain a nitrogen-doped fluorescent carbon quantum dot crude product; the crude product was filtered through a 0.22 μm filter to remove large particulate matter, and then dialyzed in a 1000Da dialysis bag for 24 hours to remove unreacted starting materials and small particulate matter. And (3) the dialyzed solution is fixed to a volume of 50mL to obtain a nitrogen doped fluorescent carbon quantum dot solution, and the solution is preserved in a dark place for later use.
As shown in FIG. 1, the nitrogen-doped fluorescent carbon quantum dot of the invention has good monodispersity and sphericity, the size distribution range is 1.2-4.6 nm, and the particle size is 2.7nm calculated by counting the average particle size of 100 particles. The presence of graphite-like carbon was confirmed by the fact that the lattice fringes of CQDs were clearly observed with a high resolution transmission electron microscope, with a lattice spacing of 0.23nm, due to the (100) graphitic plane.
As shown in FIG. 2, the nitrogen-doped fluorescent carbon quantum dots of the invention respectively show a fluorescence excitation peak at about 235nm and 327nm, which respectively correspond to sp 2 Pi-pi transition of graphite carbon core and n-pi transition of functional group such as C= O, N =O. Interestingly, the nitrogen-doped fluorescent carbon quantum dot only observed a fluorescence emission peak around 420nm, whether excited at 235nm or 327nm, a new phenomenon that may be due to n-pi conjugated functional groups and sp 2 The graphitic carbon forms a super-conjugated system. This dual excitation-single emission phenomenon provides a new strategy for the construction of fluorescence ratio sensors.
Example 2 construction of a Rate-type fluorescence sensor for Fungicide
200. Mu.L of the fluorescent carbon quantum dot prepared in example 1 was added to a series of cuvettes with 4. Mu.L, 8. Mu.L, 10. Mu.L, 12. Mu.L, 20. Mu.L, 30. Mu.L, 40. Mu.L, 60. Mu.L, 100. Mu.L, 140. Mu.L, 200. Mu.L, 300. Mu.L, 400. Mu.L, 600. Mu.L and 700. Mu.L of a solution of a phosphorus-volt standard (100. Mu.g/mL) respectively, and the volume was fixed to 5mL with a 2:3 methanol-water solution (pH 11) and shaken well. The emission wavelength was fixed at 400 to 440nm, the fluorescence excitation spectrum was scanned by LS55 type fluorescence spectrophotometer, and the excitation peak was recorded at 235nm (I 1 ) And 327nm (I) 2 ) Fluorescence intensity from left to right. I is as follows 2 /I 1 And (3) establishing a standard curve by taking the phosphorus killing concentration as an abscissa and taking the phosphorus killing concentration as an ordinate to obtain a regression equation and a linear correlation coefficient. Meanwhile, fluorescent pictures of fluorescent carbon quantum dots under the existence of different concentrations of phosphorus are observed under a 254nm ultraviolet lamp.
As shown in FIG. 3, with the continuous addition of the phosphorus, the nitrogen-doped fluorescent carbon quantum dot can respond to the phosphorus (can be stabilized for more than 1 h) within 1min, and the fluorescent excitation peak at 235nm is continuously quenched, and the blue shift of the excitation wavelength from 235nm to 220nm is accompanied, while the excitation peak at 327nm is almost unchanged. Thus, the light-emitting diode can be used at 235nm (I 1 ) The signal at 327nm (I 2 ) The signal at the position is used as a reference signal to construct the ratio-type fluorescent sensor for the phosphorus volt-killing.
As shown in FIG. 4, the ratio of excitation signals I 2 /I 1 Shows good linear relation with the concentration of the phosphorus in the range of 0.08-4.00 mu g/mL and 4.00-14.00 mu g/mL, and the linear regression equation is I respectively 2 /I 1 ＝0.18c+0.60，I 2 /I 1 =0.09c+0.89 (where c represents the concentration of phosphorus in volts), the correlation coefficient (r) is 0.9986 and 0.9990, respectively, and the detection limit is 26.67ng/mL.
As shown in FIG. 5, with the continuous addition of the phosphorus volt, the continuous quenching of the carbon quantum dots can be observed under a 254nm ultraviolet lamp, which proves that the ratio-type fluorescent sensor constructed by the invention has potential application value in the visual detection of the phosphorus volt.
Example 3 Selective investigation of a Rate-type fluorescence sensor for Fungicide
Selectivity is an important indicator for evaluating sensor performance. By detecting the ratio signal of coexisting materials and other pesticides, the selectivity of the ratio sensor based on the excitation spectrum was studied.
200. Mu.L of the nitrogen-doped fluorescent carbon quantum dot obtained in example 1 and 4.00. Mu.g/mL of the Fungicide, acetochlor, alachlor, methylparaben, pyridaben, clothianidin, dibromo-phosphorus, inner phosphorus, hexa-chlorobenzene, phoxim, cypermethrin and NO are respectively added into a series of 5mL colorimetric tubes 2- ，S - ，Cl - ，F - ，SO 4 2- ，Na + ，Al 3+ ，Cr 6+ ，Mn 2+ ，NH 4 + ，Ca 2+ And (3) using a 2:3 methanol-water solution to fix the volume to the scale marks, and respectively marking the scale marks as A to V. Fixed emission wavelength 420nm, scanning fluorescence excitation spectrum of nitrogen doped fluorescent carbon quantum dots, and recording fluorescence excitation peak I at the same time 1 And I 2 And calculating the ratio of the individual nitrogen-doped fluorescent carbon quantum dots, which is calculated as (I 2 /I 1 ) 0 The ratio in the presence of phosphorus or other interfering substances, calculated as I 2 /I 1 Fluorescence ratio change value (I 2 /I 1 ) 0 -(I 2 /I 1 )。
As shown in FIG. 6, in the presence of 4.00. Mu.g/mL of phosphorus, the difference in fluorescence change (I 2 /I 1 ) 0 -(I 2 /I 1 ) The difference value of fluorescence change in the presence of other 4.00 mug/mL interfering substances is between-0.03 and 0.182, which indicates that the dual-excitation ratio sensor constructed by the invention has the characteristics of opposite voltageThe phosphorus killing has good selectivity.
Example 4 detection of Fungicide content in lake Water
Lake water was taken from a university campus in Guangxi and allowed to stand overnight to precipitate large suspensions, which were then filtered through a 0.22 filter. 200. Mu.L of the nitrogen-doped fluorescent carbon quantum dot obtained in example 1 and 200. Mu.L of the lake water sample are taken, the volume is fixed to the scale by using a 2:3 methanol-water solution, and the samples are uniformly shaken. The emission wavelength was fixed at 420nm, and the fluorescence excitation spectrum was scanned by LS55 type fluorescence spectrophotometer, and the excitation peak was recorded at about 235nm (I 1 ) And 327nm (I) 2 ) Is a fluorescent intensity of (a) a fluorescent light. A labeling recovery experiment was performed simultaneously with a labeling level of 0.2,0.4,0.8 μg/mL. Each set of samples was assayed in parallel 6 times. Recovery and relative standard deviation RSD were calculated.
The results showed that no phosphorus was detected in the lake water of the university campus in guangxi, the recovery rates of the three addition levels were 90.64%,110.17%,104.78% respectively, and the corresponding RSDs were 5.33%,7.93%,4.02% respectively. Therefore, the photovoltaic phosphorus-killing fluorescence ratio sensor has good accuracy and precision in lake water sample detection.
Example 5 detection of Fungicide content in river water
River water was taken from the heart polder river in the nan Ning city and left to stand overnight to precipitate large suspended matter, which was then filtered through a 0.22 filter membrane. Reference example 4.
The results showed that no phosphorus is detected in the water of the polder river in the Nanning city, and the recovery rates of the three standard addition levels are 98.51%,101.08%,95.73% respectively, and the corresponding RSDs are 5.07%,5.87%,7.22% respectively. Therefore, the photovoltaic phosphorus-killing fluorescence ratio sensor has good accuracy and precision in river water sample detection.
Example 6 detection of Fungicide content in strawberry
The strawberry samples are obtained from local markets, firstly, homogenization treatment is carried out, then, 0.5-2 g of the samples are taken and added into a 10mL centrifuge tube, 4mL of methanol-water solution (2:3) is added, water bath extraction is carried out for 30min in a shaking table, centrifugation is carried out, supernatant fluid is taken, and a filter membrane with the diameter of 0.22 mu m is adopted for testing. Reference example 4.
The results show that no vomica is detected in the strawberry samples, and the results of the labeling recovery experiments show that the recovery rates of the three labeling levels are 112.74%,111.98%,98.22% respectively, and the corresponding RSDs are 5.30%,13.21% and 9.10% respectively. Therefore, the photovoltaic phosphorus killing fluorescence ratio sensor has good accuracy and precision in strawberry sample detection.
In addition, the inventor also uses cellulose and xylose as carbon sources and NH 4 HCO 3 And synthesizing the nitrogen doped fluorescent carbon quantum dot by taking dicyandiamide, ammonia water and ethylenediamine as nitrogen sources and referring to the method. Research shows that the obtained nitrogen doped fluorescent carbon quantum dot has similar structure and property, and also has double excitation-single emission fluorescent property and similar response. Nevertheless, the nitrogen-doped fluorescent carbon quantum dots synthesized by taking cellulose disaccharide as a carbon source and urea as a nitrogen source have the advantages of shortest reaction time, mild reaction temperature and strongest fluorescent property.
Claims (7)
1. The preparation method of the nitrogen-doped fluorescent carbon quantum dot visual detection ratio type fluorescent sensor for the phosphorus killing is characterized by comprising the following steps of: the nitrogen-doped fluorescent carbon quantum dot is synthesized by taking natural high molecular saccharides as a carbon source, adding a nitrogen source and adopting a one-step hydrothermal method; the nitrogen-doped fluorescent carbon quantum dot has the fluorescence characteristic of double excitation and single emission, and when the fixed emission wavelength is 400-440 nm, the nitrogen-doped fluorescent carbon quantum dot has an excitation peak at each of 235nm and 327 nm; the natural high molecular sugar is one or more of cellulose, xylose and cellobiose; the nitrogen source is one or more of urea, ammonium bicarbonate, dicyandiamide, ethylenediamine and ammonia water; the nitrogen-doped fluorescent carbon quantum dot is prepared according to the following steps: taking natural high molecular saccharides as a carbon source, adding a nitrogen source, adding deionized water into a hydrothermal reaction kettle, performing hydrothermal reaction in a high-temperature environment, and cooling to obtain a nitrogen-doped fluorescent carbon quantum dot crude product; and filtering the crude product by a filter membrane, and dialyzing by a dialysis bag to obtain a nitrogen doped fluorescent carbon quantum dot purified product.
2. A fluorescence ratio detection method of a phosphorus-killing pesticide is characterized by comprising the following steps of: preparing a gradient concentration phosphorus-volt solution by using nitrogen-doped fluorescent carbon quantum dots and phosphorus-volt standard substances, fixing the emission wavelength at 400-440 nm, scanning a fluorescence excitation spectrum by using a fluorescence spectrophotometer, recording the fluorescence intensities of excitation peaks 235nm (I1) and 327nm (I2), and establishing a standard curve by using the ratio I2/I1 of the fluorescence excitation peak intensities as an ordinate and the phosphorus-volt concentration as an abscissa; based on the standard curve, the detection of the phosphorus in the sample is realized; the nitrogen-doped fluorescent carbon quantum dot is synthesized by taking natural high molecular saccharides as a carbon source, adding a nitrogen source and adopting a one-step hydrothermal method; the nitrogen-doped fluorescent carbon quantum dot has the fluorescence characteristic of double excitation and single emission, and when the fixed emission wavelength is 400-440 nm, the nitrogen-doped fluorescent carbon quantum dot has an excitation peak at each of 235nm and 327 nm; the natural high molecular sugar is one or more of cellulose, xylose and cellobiose; the nitrogen source is one or more of urea, ammonium bicarbonate, dicyandiamide, ethylenediamine and ammonia water; the nitrogen-doped fluorescent carbon quantum dot is prepared according to the following steps: taking natural high molecular saccharides as a carbon source, adding a nitrogen source, adding deionized water into a hydrothermal reaction kettle, performing hydrothermal reaction in a high-temperature environment, and cooling to obtain a nitrogen-doped fluorescent carbon quantum dot crude product; and filtering the crude product by a filter membrane, and dialyzing by a dialysis bag to obtain a nitrogen doped fluorescent carbon quantum dot purified product.
3. The method for detecting the fluorescence ratio of a phosphorus-volt pesticide according to claim 2, wherein: the natural high molecular sugar is 0.05-0.5 g, the nitrogen source is 0.2-2.0 g, the deionized water is 10-50 mL, the hydrothermal reaction is carried out at 140-210 ℃ for 1-15 h, and the dialysis adopts a dialysis bag of 500-1000 Da for dialysis 12-36 h.
4. A method for detecting the fluorescence ratio of a pesticidal volt-ampere according to claim 3, wherein: the natural high molecular sugar is 0.2g cellulose disaccharide, the nitrogen source is 0.75g urea, the deionized water is 20mL, the hydrothermal reaction is carried out at 180 ℃ for 4h, the dialysis adopts a dialysis bag of 1000Da for 24h dialysis, and the volume of the solution after dialysis is fixed to 50mL.
5. The method for detecting the fluorescence ratio of a phosphorus-volt pesticide according to claim 4, wherein: the emission wavelength is fixed at 420-430 nm.
6. The method for detecting the fluorescence ratio of a phosphorus-volt pesticide according to claim 5, wherein: the gradient concentration of the volt-ampere phosphorus solution adopts a mixed solution of methanol and water as a solvent, and the ratio of the methanol to the water in the mixed solution of the methanol and the water is 1-4:4-1.
7. The method for detecting the fluorescence ratio of a phosphorus-volt pesticide according to claim 6, wherein: the ratio of the methanol to the water in the mixed solution of the methanol and the water is 1:4, 2:3, 3:2 or 4:1.
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