CN1441248A - Detection method of glyoxalic acid, glycolic acid, glyoxal and oxalic acid - Google Patents
Detection method of glyoxalic acid, glycolic acid, glyoxal and oxalic acid Download PDFInfo
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Abstract
The present invention relates to ionic chromatography method of detecting glyoxalic acid, glycolic acid, glyoxal and oxalic acid. The detection includes the steps of: weighing sodium carbonate and sodium bicarbonate and dissolving with deionized water to compound eluting liquid; weighing sodium hydroxide and dissolving with deionized water to compound eluting liquid; weighing sodium hydroxide and dissolving with deionized water to compound eluting liquid; diluting the sample with deionized water to concentration for detection and ionic chromatography detection; comparing the ionic chromatography detection result of the sample with corresponding standard work curve to obtain the composition and contents of the sample. The said method can fast detecting the said components simultaneously in high selectivity and high sensitivity.
Description
(1) technical field
The present invention relates to a kind of method that adopts the ion chromatograph conductance detection method to detect glyoxalic acid, glycollic acid, glyoxal and oxalic acid.
(2) background technology
Glyoxalic acid (CHOCOOH) is the simplest aldehydic acid, has two kinds of character of aldehyde and acid concurrently.Glyoxalic acid can derive tens kinds of fine chemical products, can be used as the intermediate of spices, medicine, agricultural chemicals, paint, amino acid fine chemical product; The crosslinking chemical that also can be used for processes such as water paint, surfactant, food storage and Polymer Synthesizing.Along with the development in glyoxalic acid downstream product market, it has become a kind of fine chemical product with fine development prospect, and has at home and abroad obtained using widely.The synthetic method of glyoxalic acid can be divided into chemical method and electrosynthesis.Chemical method just progressively is eliminated because environmental pollution is serious and expensive raw material price.Characteristics such as electrosynthesis has that raw material is cheap and easy to get, flow process is simple, accessory substance is few, product separates easily, quality height, reaction conditions gentleness, cost is low and environmental pollution is little have become glyoxalic acid synthetic important channel and developing direction.In electric building-up process, the main species of reactant liquor and Generation Liquid comprise: glyoxalic acid, glycollic acid, oxalic acid and glyoxal, and wherein glyoxalic acid is a principal product, other then is accessory substance or reactant.Synthetic process evaluation and operation instruction all have great importance the detection by quantitative of glyoxalic acid to electricity.But since glyoxalic acid, glycollic acid, oxalic acid and glyoxal molecular structure closely similar, also be that they all contain groups such as carboxyl or aldehyde radical, phase mutual interference between the species is very big, does not also have a kind of method for separating and detecting efficiently that is suitable for actual industrial process so far.
In actual detected, people still have to adopt the loaded down with trivial details chemical analysis of operation steps to be measured at present.(Du Zhiping explains young minister in ancient times, appoints intelligent as Du Zhi equality, Deng, potentiometric titration is used for the analysis of glyoxalic acid, chemistry world, 2002, (4): 181-184) utilization potentiometric titration, though this method is simple, because water is protolytic solvent, its specific inductive capacity is big, acidic species in the reactant liquor is had stronger leveling effect, thereby cause first hop of titration curve extremely not obvious, therefore be difficult to obtain satisfied result.(Xu Jialiang such as Xu Jia cold, Wang Chengyu, Tang Xiaodong, dual wavelength and three wavelength spectrophotometry are measured glyoxalic acid and glyoxal, analytical chemistry, 1997 simultaneously, (9): 1086-1089) adopt spectrophotometric method, because sample does not have light absorption or absorbs very weakly in that visible or ultraviolet light is regional, makes its generation chromogenic reaction so must add developer, promptly is created on the material that absorption can be arranged in this determination limit yet.Generally select 2,4 dinitrophenyl hydrazine for use, generate glyoxalic acid hydrazone class material with glyoxalic acid generation chromogenic reaction earlier, and then the assay determination of being correlated with.Need the long time because glyoxalic acid and 2,4 dinitrophenyl hydrazine reaction will all be converted into the glyoxalic acid hydrazone, so whole analytical cycle is longer, error is bigger.This method needs number of chemical reagent, and sensitivity is low and interference arranged.(Hu Jun, Zhang Xinsheng, Wu Mingdong such as Hu Jun, Deng, the chemical analysis method of glyoxal anodic oxidation system glyoxalic acid process, East China University of Science's journal, 2001, (1): 34-37) utilization chemical analysis, its defective is that operation steps is loaded down with trivial details, during check fee, be subject to disturb, resultant error is big.When the electrolytic solution in the electric building-up process was measured, oxalic acid quantitative needed earlier to measure with permanganimetric method with behind the calcium precipitation again; Glyoxal the quantitative Tuscany of utilization earlier use the standard acidity test again after looking into Luo Fanying; The aldehyde total amount is then measured with Arbiso process, and glyoxalic acid quantitatively can only adopt the aldehyde total amount deduct glyoxal amount try to achieve; Equally, the content of glycollic acid also has only the amount that deducts oxalic acid and glyoxalic acid by sour total amount just can try to achieve in the sample.High performance liquid chromatography is the new technology of a kind of ion analysis of just growing up the seventies in 20th century.This method has highly sensitive, and therefore the advantage that error is little is subjected to common concern.Report mainly is reversed-phase high-performance liquid chromatography at present, as (Zhou Xin, Zhao Zhichao, Zhang Yanjie such as Zhou Xin, Deng, reversed phase ion separates the discussion of glyoxalic acid derivative mechanism, Qingtao Chemical Engineering College's journal, 1998 to high performance liquid chromatography, (1): 67-69) during the glyoxalic acid in measuring electrolytic solution, sample equally must be earlier behind the 2,4 dinitrophenyl hydrazine derivatization, again with tetrabutyl ammonium bromide for the reversed-phased high performace liquid chromatographic of ion reagent is measured.Its shortcoming is that sample pre-treatments still needs number of chemical reagent, still can't overcome signal interference and spectra overlapping phenomenon than complex system.Simultaneously required equipment is quite expensive.
(3) summary of the invention
The present invention aim to provide a kind of adopt the ion chromatograph conductance detection method easy, detect the method for glyoxalic acid, glycollic acid, glyoxal and oxalic acid fast, simultaneously.
The said detection method step of the present invention is as follows:
1, preparation eluent: weighing sodium carbonate and sodium bicarbonate, with deionized water dissolving and be mixed with and contain 0.8～7.2mmol/LNa
2CO
3+ 1.0～9.0mmol/L NaHCO
3Aqueous solution, be designated as A
#Eluent.
2, preparation eluent: weighing sodium hydroxide is mixed with 0.5～4.0mmol/L NaOH+0.01～0.2mmol/L Na with deionized water
2CO
3Mixed liquor is designated as B
#Eluent.
3, with deionized water sample is diluted to the detectable scope of ion chromatograph conductance pick-up unit, carries out chromatography of ions by the ion chromatograph conductance detection method and detect.
4, the chromatography of ions testing result and the corresponding standard working curve of sample are contrasted, and tried to achieve the composition and the content of sample respectively.
Said A
#Eluent can be mixed with and contains 2.0～2.8mmol/L Na
2CO
3+ 2.5～3.5mmol/L NaHCO
3Aqueous solution, be preferably and contain 2.4～2.8mmol/L Na
2CO
3+ 3.0～3.5mmol/L NaHCO
3Aqueous solution.Said B
#Eluent can be mixed with and contains 1～2mmol/L NaOH+0.05～0.1mmol/L Na
2CO
3Mixed liquor.
In the time of adopting the ion chromatograph conductance detection method to detect glyoxalic acid, glycollic acid, oxalic acid and glyoxal, not only can show the selectivity height, detect sensitive, fast, the advantage that equipment is easy relatively, and can reach simultaneously, the purpose of fast measuring various ingredients.Wherein some ion still is to be difficult to adopt other method to finish detection at present.Experimental result shows, the composition, the particularly quantitative measurement to the principal product glyoxalic acid of ion chromatograph conductance detection method of the present invention electrolytic solution (being the mixed liquor of glyoxalic acid, glycollic acid, glyoxal and oxalic acid) in the detection electricity synthesizes fast, have simultaneously been obtained good effect.Therefore, the advantage of ion chromatograph conductance detection method not only is embodied in quick, sensitive that single species detects, and be to provide a kind of quick, easy detection method for analysis, control that dynamo-electric synthesizing glyoxalic acid process is arranged, this has much realistic meaning to the development that dynamo-electric compound probability is arranged.Relevant experimental result can be able to further instruction from following embodiment.
(4) description of drawings
Fig. 1 is a standard ionomer chromatograph conductance pick-up unit process flow diagram.
Fig. 2 is the standard working curve that embodiment 1 utilization ion chromatograph conductance detection method detects glyoxalic acid.
Fig. 3 is the standard working curve that embodiment 2 utilization ion chromatograph conductance detection methods detect glycollic acid.
Fig. 4 be embodiment 3 utilization ion chromatograph conductance detection methods detect glyoxals standard working curve.
Fig. 5 is the chromatography of ions figure that embodiment 4 utilization ion chromatograph conductance detection methods detect glyoxalic acid and oxalic acid.
Fig. 6 is the chromatography of ions figure that embodiment 5 utilization ion chromatograph conductance detection methods detect glycollic acid and oxalic acid.
Fig. 7 is the chromatography of ions figure that embodiment 6 utilization ion chromatograph conductance detection methods detect glyoxalic acid and glycollic acid.
Fig. 8 be embodiment 7 utilization ion chromatograph conductance detection methods detect glyoxals chromatography of ions figure.
Fig. 9 detects the chromatography of ions figure of actual electrolytic solution for embodiment 8 utilization ion chromatograph conductance detection methods.
(5) embodiment
Following embodiment will the present invention is further illustrated in conjunction with the accompanying drawings.
Embodiment 1: under given chromatographic condition, i.e. and YSA type 8098A-2
#Anion chromatographic column (Beijing chemical industry metallurgical research institute of Ministry of Nuclear Industry system); PCD-1 pulse electric conductivity detector (Xiamen University's system); G-XYZ-A galvanochemistry suppressed column (Xiamen University's system); A
#Eluent: 2.4mmol/L Na
2CO
3+ 3.0mmol/L NaHCO
3Flow velocity: 1.5mL/min; Sample size: 100 μ L.By the filter membrane sample introduction, inject the glyoxalic acid standard solution of 100 μ L variable concentrations with the rotation six-way valve respectively, carry out chromatography of ions by experimental technique and detect.Can adopt the flow process as the standard ionomer chromatogram arrangement of Fig. 1, it is made up of drip washing liquid bath 1, constant-flux pump 2, sampling valve 3, separating column 4, suppressed column 5, electric conductivity detector 6 and registering instrument 7 etc.Drip washing liquid bath 1, constant-flux pump 2, sampling valve 3 are formed the transport portion of ion chromatograph, and separating column is a separating part, and suppressed column and electric conductivity detector are formed the test section, and registering instrument etc. are handled experimental data.The result as shown in Figure 2.From Fig. 2, can clearly find out the glyoxalic acid concentration M/mgL that adopts the present invention to measure
-1And between its standard ionomer chromatographic peak intensity A, show good linear relationship in 5.0～30.0mg/L concentration range.Equation of linear regression is Y=-5.705+3.230X, linear regression coeffficient R=0.9992.
Embodiment 2: identical with the method for embodiment 1, the standard working curve that injection glycollic acid standard solution obtains as shown in Figure 3.From Fig. 3, can clearly find out the glycollic acid concentration M/mgL that adopts this method to measure
-1And the linear relationship between its standard ionomer chromatographic peak intensity A, the range of linearity are at 2.0～35.0mg/L, and equation of linear regression is Y=-0.9546+3.5883X, linear regression coeffficient R=0.9996.Adopt B
#Eluent: 2.0mmol/L NaOH+0.05mmol/L Na
2CO
3, flow velocity is identical with embodiment 1 with sample size.
Embodiment 3: identical with the method for embodiment 1, the standard working curve that injection glyoxal standard solution obtains as shown in Figure 4.From Fig. 4, can clearly find out, adopt the glyoxal concentration of this method mensuration and the linear relationship between its standard ionomer chromatographic peak intensity A, the range of linearity is at 5.0～25.0mg/L, and equation of linear regression is Y=1.2948+1.7854X, linear regression coeffficient R=0.9992.Adopt B
#Eluent, flow velocity, sample size are identical with embodiment 2.
Embodiment 4: Fig. 5 provides the chromatography of ions figure of glyoxalic acid and oxalic acid.From Fig. 5, can clearly find out, when sample is single species glyoxalic acid or oxalic acid, 1 peak (Fig. 5 a, 0.2mmol/L oxalic acid, or Fig. 5 b, 0.2mmol/L glyoxalic acid) in its chromatography of ions figure, only occur; If when sample is the mixed liquor of glyoxalic acid and oxalic acid, at corresponding elution time place 2 peaks (Fig. 5 c, 0.2mmol/L oxalic acid+0.2mmol/L glyoxalic acid) appear then, show that this assay method has good selectivity to detecting glyoxalic acid and oxalic acid.Adopt the A# eluent identical with embodiment 1.Horizontal ordinate is retention time/second (t/s) in Fig. 5, and ordinate is that electricity is led/little Siemens (G/ μ s).
Embodiment 5: Fig. 6 provides the chromatography of ions figure of glycollic acid and oxalic acid.Equally, when sample is single species glycollic acid or oxalic acid, 1 peak (Fig. 6 a, 0.2mmol/L oxalic acid, or Fig. 6 b, 0.25mmol/L glyoxalic acid) only appears in its chromatography of ions figure; If when sample is the mixed liquor of glycollic acid and oxalic acid, at corresponding elution time place 2 peaks (Fig. 6 c, 0.2mmol/L oxalic acid+0.2mmol/L glyoxalic acid) appear then, show that this assay method has good selectivity to detecting glycollic acid and oxalic acid.In Fig. 6, coordinate is identical with Fig. 5.
Embodiment 6: Fig. 7 is the chromatography of ions figure of glycollic acid and glyoxalic acid.Can find out clearly that from Fig. 72 peak a occur at corresponding elution time place, b is corresponding glycollic acid and glyoxalic acid respectively, and the elution time of peak position from relatively open, show that this assay method has good selectivity to detecting glycollic acid and oxalic acid.Adopt B
#Eluent, flow velocity, sample size are identical with embodiment 2.
Embodiment 7: when Fig. 8 provides different eluent glyoxal testing result.Wherein Fig. 8 a is 2.4mmol/L Na
2CO
3+ 3.0mmol/L NaHCO
3(be A
#Eluent), Fig. 8 b is 2.0mmol/L NaOH+0.10mmol/L Na
2CO
3(be B
#Eluent).From Fig. 8 a, as seen, can only see that other places do not observe the spectrum peak outside the negative sense spectrum peak corresponding to water sample; But if use B instead
#Eluent then effect is completely different, among the figure except that the water sample peak, also have one very tangible corresponding to glyoxal spectrum peak (seeing Fig. 8 b).
Embodiment 8: the utilization chromatography of ions to the chromatography of ions testing result of actual electrolytic solution as shown in Figure 9.From Fig. 9, can observe, 2 peak a occur at the elution time place of corresponding glycollic acid and glyoxalic acid, b, and also the peak position branch is fairly good.In addition, the c peak is corresponding to the spectrum peak of oxalic acid, and the d peak is corresponding to the spectrum peak of water.Horizontal ordinate is retention time/second (t/s), and ordinate is that electricity is led/little Siemens (G/ μ s).In addition, also the recovery to several species detects, and the result shows that greater than 98% the present invention has good effect to detecting actual electrolytic solution.
Embodiment 9: preparation A
#The method of eluent: take by weighing 6.36g and analyze pure sodium carbonate and 6.30g and analyze pure sodium bicarbonate and in beaker, dissolve, insert in the 500mL volumetric flask and be settled to scale, be 120mmol/L Na with deionized water
2CO
3+ 150mmol/L NaHCO
3Aqueous solution.Pipette an amount of above-mentioned solution and add deionized water, be mixed with and contain 0.8～7.2mmol/L Na
2CO
3+ 1.0～9.0mmol/LNaHCO
3Aqueous solution, also promptly obtain A
#Eluent.
Embodiment 10: preparation B
#The method of eluent: take by weighing and analyze pure cerium hydroxide sodium, add the aqueous solution that deionized water is mixed with 10mmol/LNaOH.Pipette an amount of 10mmol/L Na
2CO
3Solution adds in this solution, makes 0.5～4.0mmol/LNaOH+0.01～0.2mmol/L Na
2CO
3Mixed liquor also promptly obtains B
#Eluent.
Embodiment 11: the preparation of standard solution and the method for drafting of standard working curve:
A) preparation of glyoxalic acid standard solution: in the 100mL volumetric flask, get 200mg/L OHC-COOH. solution with the deionized water constant volume with the 0.9328g glyoxalic acid; Pipette this solution 25.0mL in the 100mL volumetric flask, constant volume gets the 50.0mg/L glyoxylic acid solution; Pipette 2.5,5.0,7.5,10.0,12.5 respectively from the 50.0mg/L glyoxylic acid solution, 15.0mL is in the 25mL volumetric flask, and constant volume gets 5.0,10.0,15.0,20.0,25.0,30.0mg/L glyoxalic acid standard solution.
B) preparation of glycollic acid standard solution: pipette 0.5mol/L glycollic acid mother liquor in the 100mL volumetric flask, constant volume gets the 40.0mmol/L glycollic acid; The glycollic acid solution that pipettes 1mL40mmol/L gets the 0.40mmol/L glycollic acid in 100mL volumetric flask constant volume; Pipette an amount of 0.40mmol/L glycollic acid solution respectively in the 25mL volumetric flask, constant volume gets 1.0,2.0,4.0,8.0,16.0,24.0, the 32.0mg/L glyoxylic acid solution.
C) preparation of glyoxal standard solution: pipette an amount of 6.8mmol/L glyoxal water solution respectively in the 50mL volumetric flask, constant volume gets 5.8,8.7,11.6,14.5,17.4,20.3,23.2mg/L glyoxal standard solution.
D), the drafting of working curve: under given chromatographic condition, extract the above-mentioned standard solution of 100 μ L respectively, carry out chromatography of ions by experimental technique and detect.Fig. 2, Fig. 3 and Fig. 4 provide respectively glyoxalic acid, glycollic acid and glyoxal standard working curve.Also can draw out the standard working curve (figure slightly) of oxalic acid similarly.
Claims (9)
1, the detection method of glyoxalic acid, glycollic acid, glyoxal and oxalic acid is characterized in that said detection method step is as follows:
1), the preparation eluent: weighing sodium carbonate and sodium bicarbonate, with deionized water dissolving and be mixed with and contain 0.8～7.2mmol/LNa
2CO
3+ 1.0～9.0mmol/L NaHCO
3Aqueous solution, be designated as A
#Eluent;
2), preparation eluent: weighing sodium hydroxide is mixed with 0.5～4.0mmol/L NaOH+0.01～0.2mmol/L Na with deionized water
2CO
3Mixed liquor is designated as B
#Eluent;
3), with deionized water sample is diluted to the detectable scope of ion chromatograph conductance pick-up unit, carrying out chromatography of ions by the ion chromatograph conductance detection method detects;
4), the ion chromatograph conductance testing result and the corresponding standard working curve of sample are contrasted, and try to achieve the composition and the content of sample respectively.
2, the detection method of glyoxalic acid as claimed in claim 1, glycollic acid, glyoxal and oxalic acid is characterized in that said A
#Eluent is mixed with and contains 2.0～2.8mmol/L Na
2CO
3+-2.5～3.5mmol/L NaHCO
3Aqueous solution.
3, the detection method of glyoxalic acid as claimed in claim 1, glycollic acid, glyoxal and oxalic acid is characterized in that said A
#Eluent is mixed with and contains 2.4～2.8mmol/L Na
2CO
3+ 3.0～3.5mmol/L NaHCO
3Aqueous solution.
4, the detection method of glyoxalic acid as claimed in claim 1, glycollic acid, glyoxal and oxalic acid is characterized in that said B
#Eluent is mixed with and contains 1～2mmol/L NaOH+0.05～0.1mmol/L Na
2CO
3Mixed liquor.
5, the detection method of glyoxalic acid as claimed in claim 1, glycollic acid, glyoxal and oxalic acid is characterized in that preparing A
#The method of eluent: take by weighing 6.36g and analyze pure sodium carbonate and 6.30g and analyze pure sodium bicarbonate and in beaker, dissolve, insert in the 500mL volumetric flask and be settled to scale, be 120mmol/L Na with deionized water
2CO
3+ 150mmol/L NaHCO
3Aqueous solution; Pipette an amount of this solution and add deionized water, be mixed with and contain 0.8～7.2mmol/L Na
2CO
3+ 1.0～9.0mmol/L NaHCO
3Aqueous solution, promptly obtain A
#Eluent.
6, the detection method of glyoxalic acid as claimed in claim 1, glycollic acid, glyoxal and oxalic acid is characterized in that preparing B
#The method of eluent: take by weighing and analyze pure cerium hydroxide sodium, add the aqueous solution that deionized water is mixed with 10mmol/L NaOH; Pipette an amount of this solution and add in this solution, make 0.5～4.0mmol/L NaOH+0.01～0.2mmol/L Na
2CO
3Mixed liquor promptly obtains B
#Eluent.
7, the detection method of glyoxalic acid as claimed in claim 1, glycollic acid, glyoxal and oxalic acid, the compound method that it is characterized in that said glyoxalic acid standard solution: in the 100mL volumetric flask, get the 200mg/L glyoxylic acid solution with the deionized water constant volume with the 0.9328g glyoxalic acid; Pipette this solution 25.0mL constant volume in the 100mL volumetric flask and get the 50.0mg/L glyoxylic acid solution; Pipette 2.5,5.0,7.5,10.0,12.5 respectively from the 50.0mg/L glyoxylic acid solution, 15.0mL is in the 25mL volumetric flask, and constant volume gets 5.0,10.0,15.0,20.0,25.0,30.0mg/L glyoxalic acid standard solution.
8, the detection method of glyoxalic acid as claimed in claim 1, glycollic acid, glyoxal and oxalic acid, the compound method that it is characterized in that said glycollic acid standard solution: pipette 0.5mol/L glycollic acid mother liquor constant volume in the 100mL volumetric flask, get the 40.0mmol/L glycollic acid, the glycollic acid solution that pipettes 1mL40mmol/L gets the 0.40mmol/L glycollic acid in 100mL volumetric flask constant volume; Pipette an amount of 0.40mmol/L glycollic acid solution respectively in the 25mL volumetric flask, constant volume gets 0.95,1.90,3.80,7.60,15.2,22.8, the 30.4mg/L glyoxylic acid solution.
9, the detection method of glyoxalic acid as claimed in claim 1, glycollic acid, glyoxal and oxalic acid, the compound method that it is characterized in that said glyoxal standard solution: pipette an amount of 6.8mmol/L glyoxal water solution respectively in the 50mL volumetric flask, constant volume gets 5.8,8.7,11.6,14.5,17.4,20.3,23.2mg/L glyoxal standard solution.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100383524C (en) * | 2006-03-30 | 2008-04-23 | 上海大学 | Analysis method while alcohol, aldehyde, acetic acid, nitroethane and N,N-diethylated hydroxylammonium hydroxylamine common existing |
| CN101493417B (en) * | 2008-01-22 | 2012-01-11 | 华东理工大学 | Simple method for detecting concentration of oxalic acid |
| CN102735774A (en) * | 2012-07-10 | 2012-10-17 | 江南大学 | Method for detecting content of oxalic acid in yellow millet wine by reversed-phase high-performance liquid chromatography |
| CN103403548A (en) * | 2010-12-23 | 2013-11-20 | 梅坦诺米克斯保健有限公司 | Means and method for predicting diabetes |
| CN106198794A (en) * | 2016-07-06 | 2016-12-07 | 湖北省宏源药业科技股份有限公司 | A kind of method using chromatography analysis oxoacetic acid product |
| CN110887930A (en) * | 2019-12-19 | 2020-03-17 | 江苏泰洁智邦检测技术有限公司 | Method for measuring oxalic acid content in workplace |
| CN110927324A (en) * | 2019-12-26 | 2020-03-27 | 广州医科大学附属第一医院 | Method for simultaneously detecting concentration of glycolic acid and hippuric acid in human urine |
| CN114324727A (en) * | 2021-11-25 | 2022-04-12 | 上海浦景化工技术股份有限公司 | Method for detecting upper limit of total migration volume of glycolic acid and oligomers thereof in PGA food packaging material |
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2003
- 2003-04-10 CN CN 03109958 patent/CN1188701C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100383524C (en) * | 2006-03-30 | 2008-04-23 | 上海大学 | Analysis method while alcohol, aldehyde, acetic acid, nitroethane and N,N-diethylated hydroxylammonium hydroxylamine common existing |
| CN101493417B (en) * | 2008-01-22 | 2012-01-11 | 华东理工大学 | Simple method for detecting concentration of oxalic acid |
| CN103403548A (en) * | 2010-12-23 | 2013-11-20 | 梅坦诺米克斯保健有限公司 | Means and method for predicting diabetes |
| CN102735774A (en) * | 2012-07-10 | 2012-10-17 | 江南大学 | Method for detecting content of oxalic acid in yellow millet wine by reversed-phase high-performance liquid chromatography |
| CN106198794A (en) * | 2016-07-06 | 2016-12-07 | 湖北省宏源药业科技股份有限公司 | A kind of method using chromatography analysis oxoacetic acid product |
| CN110887930A (en) * | 2019-12-19 | 2020-03-17 | 江苏泰洁智邦检测技术有限公司 | Method for measuring oxalic acid content in workplace |
| CN110927324A (en) * | 2019-12-26 | 2020-03-27 | 广州医科大学附属第一医院 | Method for simultaneously detecting concentration of glycolic acid and hippuric acid in human urine |
| CN114324727A (en) * | 2021-11-25 | 2022-04-12 | 上海浦景化工技术股份有限公司 | Method for detecting upper limit of total migration volume of glycolic acid and oligomers thereof in PGA food packaging material |
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