CN101451980B - High performance liquid chromatography method for detecting glyoxal, glyoxylic acid and acetaldehyde - Google Patents
High performance liquid chromatography method for detecting glyoxal, glyoxylic acid and acetaldehyde Download PDFInfo
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- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 title claims abstract description 158
- 229940015043 glyoxal Drugs 0.000 title claims abstract description 112
- 238000004128 high performance liquid chromatography Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 21
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims abstract description 49
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- 238000005303 weighing Methods 0.000 claims description 7
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
- 238000010790 dilution Methods 0.000 claims description 4
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- 238000012546 transfer Methods 0.000 claims description 4
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- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000012488 sample solution Substances 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 14
- 238000007254 oxidation reaction Methods 0.000 abstract description 14
- 239000007795 chemical reaction product Substances 0.000 abstract description 4
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- 238000000825 ultraviolet detection Methods 0.000 abstract 1
- 230000014759 maintenance of location Effects 0.000 description 16
- PRRPUEWAMYRKPC-UHFFFAOYSA-N 2-hydroxyiminoacetaldehyde Chemical compound ON=CC=O PRRPUEWAMYRKPC-UHFFFAOYSA-N 0.000 description 15
- 239000007788 liquid Substances 0.000 description 13
- 238000001228 spectrum Methods 0.000 description 13
- 238000012417 linear regression Methods 0.000 description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 11
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 9
- 239000001632 sodium acetate Substances 0.000 description 9
- 235000017281 sodium acetate Nutrition 0.000 description 9
- PBZUAIHRZUBBAJ-IWQZZHSRSA-N (2z)-2-hydroxyiminoacetic acid Chemical compound O\N=C/C(O)=O PBZUAIHRZUBBAJ-IWQZZHSRSA-N 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
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- -1 oxalic acid aldehyde Chemical class 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- FZENGILVLUJGJX-NSCUHMNNSA-N (E)-acetaldehyde oxime Chemical compound C\C=N\O FZENGILVLUJGJX-NSCUHMNNSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
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- LJHFIVQEAFAURQ-UHFFFAOYSA-N glyoxime Chemical compound ON=CC=NO LJHFIVQEAFAURQ-UHFFFAOYSA-N 0.000 description 5
- 150000001299 aldehydes Chemical class 0.000 description 4
- 235000006408 oxalic acid Nutrition 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 150000002923 oximes Chemical class 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
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- HORQAOAYAYGIBM-UHFFFAOYSA-N 2,4-dinitrophenylhydrazine Chemical compound NNC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O HORQAOAYAYGIBM-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- UHEQUEPSIOPIRJ-UHFFFAOYSA-N acetaldehyde;nitric acid Chemical compound CC=O.O[N+]([O-])=O UHEQUEPSIOPIRJ-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
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- 238000005705 Cannizzaro reaction Methods 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Investigating Or Analysing Biological Materials (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention relates to a High Performance Liquid Chromatography (HPLC) method for detecting glyoxal, glyoxylic acid and acetaldehyde. The detection steps are as follows: taking a proper amount of sample, adding hydroxylamine hydrochloride serving as a derivative reagent with the aldehyde group molar ratio of 1.5: 1-50: 1, reacting for 10-120 minutes at 10-80 ℃, and analyzing the obtained oximated derivative by using HPLC, wherein the ultraviolet detection wavelength is 20-300 nm. The HPLC analysis conditions were as follows: the mobile phase is acetonitrile/water solution with the volume ratio of 5/95-60/40, the flow rate is 0.6-2 ml/min, the column temperature is 20-50 ℃, and the sample injection amount is 1-20 mu L. The method has the advantages of convenience in operation, high automation degree, high selectivity and the like, and can be used for simultaneously measuring a plurality of components. The experimental result shows that when the mixture of the glyoxal, the glyoxylic acid and the acetaldehyde is measured, the detection of all the components cannot be interfered with each other; all compositions in the reaction product from the oxidation of acetaldehyde to glyoxal can be detected.
Description
Technical field
The present invention relates to a kind of high performance liquid chromatography detect glyoxal, the method for glyoxalic acid, acetaldehyde, especially relate to a kind of employing oxammonium hydrochloride and derive, detect glyoxal, the high performance liquid chromatography of glyoxalic acid, acetaldehyde.Belong to chemical analysis and instrument analysis technology field in the chemical industry.
Background technology
Glyoxal (glyoxal) claim oxalic acid aldehyde again, it is the simplest α-dicarbonyl compound, contain two interconnective carbonyls in the molecule, except the general character with fatty aldehyde, also have some special chemical property, can with alcohol, amine, acid amides, the compound of aldehyde and hydroxyl etc. carries out addition or condensation reaction, can also with albuminoid animal glue, cellulose, cross-linking reaction takes place in polyvinyl alcohol (PVA) and urea etc., be a kind of purposes industrial chemicals and intermediate very widely, in papermaking, textile printing and dyeing, coating, medicine, building materials, petrochemical industry, aspects such as environmental protection all have a wide range of applications.
At present, produce glyoxal technology and mainly contain two kinds of ethylene glycol vapour phase oxidation process and acetaldehyde nitric acid oxidation methods.Ethylene glycol air oxidation process process is simple, and product yield is higher, but raw materials cost is higher relatively, and contains formaldehyde in the product, is difficult to satisfy the requirement of industries such as medicine.The acetaldehyde nitric acid oxidation method cost of raw material is low, and reaction conditions gentleness, outstanding advantage are not contain formaldehyde in the product, can satisfy the requirement of industries such as medicine, spices and daily-use chemical industry, receives much attention in recent years.Yet, about acetaldehyde oxidation produce glyoxal the detection by quantitative of product and accessory substance, industrial all be all the time adopt traditional chemical analysis measure glyoxal, acetaldehyde and organic acid content, operation is many, more consuming time, qualitative and quantitative instrument analytical method to each product of course of reaction is still unresolved, and the research that detects each product does not especially simultaneously appear in the newspapers as yet.
In recent years, some scholar to glyoxal, the analysis of glyoxalic acid studies, as (Hu Jun such as Hu Jun, Zhang Xinsheng, Wu Mingdong, Deng. the chemical analysis method of glyoxal anodic oxidation system glyoxalic acid process. East China University of Science's journal, 2001,27 (1): the 34-37) glyoxal content in the electrolytic solution of employing Cannizzaro reaction mensuration glyoxal anodic oxidation system glyoxalic acid, the aldehyde total amount is measured with Arbiso process, glyoxalic acid quantitative with the aldehyde total amount deduct glyoxal amount, during check fee, interference and error be all bigger; (Xu Jialiang such as Xu Jia cold, Jiang Xiangdong, Tang Xiaodong, etc. the research of determined by ultraviolet spectrophotometry glyoxal content. assay office, 1998,17 (5): 41-44) adopt the determined by ultraviolet spectrophotometry glyoxal content, obtained certain effect, but ultraviolet spectrophotometry directly perceived inadequately, be subject to disturb, and glyoxal and azanol reaction only generate glyoxal dioxime, and not having a generation of glyoxal monoxime, this conclusion remains textual criticism in theory.(Shigehisa Uchiyama such as Shigehisa Uchiyama, Erika Matsushima, Hiroshi Tokunaga, et.al.Determination oforthophthalaldehyde in air using 2,4-dinitrophenylhydrazine-impregnated silicacartridge and high-performance liquid chromatography.Journal of Chromatography A, 2006, (1116): 165-171.) adopt 2,4-dinitrophenylhydrazine (DNPH) detects airborne phthalic aldehyde as derivative reagent, because aldehyde material and 2, the 4-dinitrophenylhydrazine reaction all is converted into 2, and the 4-dinitrophenylhydrazone needs the very long reaction time, and analytical cycle is longer, and 2, the 4-dinitrophenylhydrazine has certain toxicity, and poor stability is not easy to operate.How to analyze accurately and effectively glyoxal, each components contents in the glyoxalic acid, acetaldehyde mixed liquor is a technical matters that needs to be resolved hurrily.
Summary of the invention
The object of the present invention is to provide a kind of fast, accurately, and can detect individually or simultaneously glyoxal, the HPLC analytical method of glyoxalic acid, acetaldehyde, grow to remedy existing analytical approach sense cycle, can not analyze simultaneously, deficiency such as detection by quantitative.
Technical scheme of the present invention is: a kind of glyoxal, high performance liquid chromatography (HPLC) detection method of glyoxalic acid, acetaldehyde, and concrete steps are as follows:
The drafting of A, glyoxal typical curve
1), the preparation of glyoxal standard solution: get an amount of glyoxal solution with transfer pipet, respectively with the deionized water dilution, and constant volume, prepare the glyoxal standard solution of 5～7 concentration between 0.1g/L～2g/L;
2), the preparation of derivative reagent: take by weighing the appropriate hydrochloric acid azanol, with deionized water dissolving prepare 1～10g/L oxammonium hydrochloride solution;
3), glyoxal is derived and is produced the oximate sample: the above-mentioned glyoxal standard solution of getting equal volume, variable concentrations respectively, adding concentration respectively is the excessive oxammonium hydrochloride solution of 1～10g/L, the mol ratio of oxammonium hydrochloride and aldehyde radical is 1.5: 1～50: 1, after regulating pH and be 4～5 with salt of weak acid solution, with all samples volume-adjustment unanimity, under 10～80 ℃, reacted 10～120 minutes, obtain glyoxal oximate derivant;
4), preparation pH is 2～5 deionized water, with trifluoroacetic acid aqueous solution as liquid analysis of spectrum moving phase;
5), with efficient liquid phase chromatographic analysis above-mentioned steps 3) the glyoxal oximate derivant sample of the variable concentrations prepared, adopt UV-detector, chromatographic condition is:
Chromatographic column: ZORBAX Eclipse XDB-C
18, 5 μ m, 4.6 * 250mm;
Moving phase: the volume ratio of acetonitrile and water is 5/95～60/40;
Flow velocity: 0.6～2ml/min;
Column temperature: 20～50 ℃;
Sample size: 1～20 μ L;
Detect wavelength: 200～300nm.
6), concentration is mapped, with the response peak area of the glyoxal oximate derivant of variable concentrations obtain glyoxal typical curve;
The drafting of B, glyoxalic acid typical curve
1), the preparation of glyoxalic acid standard solution: take by weighing the glyoxalic acid sample of different quality respectively, use deionization
Water-soluble separating, and constant volume are prepared 5～7 concentration and are the glyoxalic acid standard solution between 0.01g/L～1g/L.
2), according in the steps A 2) preparation steps preparation oxammonium hydrochloride;
3), glyoxalic acid is derived and is produced the oximate sample: get with steps A in 3) glyoxal standard solution volume identical, above-mentioned steps 1) the glyoxalic acid standard solution of the variable concentrations of preparation in, add with steps A in 3) oxammonium hydrochloride that volume is identical, after regulating pH and be 4～5 with salt of weak acid solution, with all samples volume-adjustment unanimity, under 10～80 ℃, reacted 10～120 minutes, obtain glyoxalic acid oximate derivant;
4), among employing and the A 4)～6) same step draws the typical curve of glyoxalic acid;
The drafting of C, acetaldehyde typical curve
1), the preparation of acetaldehyde standard solution: pipette an amount of acetaldehyde solution with transfer pipet, respectively with the deionized water dilution, and constant volume, prepare the acetaldehyde standard solution of 5～7 concentration between 5g/L～100g/L;
2), the preparation of derivative reagent: take by weighing oxammonium hydrochloride, with deionized water dissolving prepare 10～100g/L oxammonium hydrochloride solution;
3), acetaldehyde is derived and is produced the oximate sample: get with steps A in 3) glyoxal standard solution volume identical, above-mentioned steps 1) in the above-mentioned acetaldehyde standard solution of variable concentrations of preparation, add with steps A in 3) 10～100g/L oxammonium hydrochloride that volume is identical, after regulating pH and be 4～5 with salt of weak acid solution, with all samples volume-adjustment unanimity, under 10～80 ℃, reacted 10～120 minutes, and obtained acetaldehyde oximate derivant;
4), among employing and the A 4)-6) same step draws the typical curve of acetaldehyde;
The deriving and detect of D, unknown concentration sample
1), according in the steps A 2) preparation steps preparation oxammonium hydrochloride;
2), get with steps A in 3) the glyoxal that contains unknown concentration that volume is identical, glyoxalic acid, acetaldehyde mixed solution, add with steps A in 3) oxammonium hydrochloride of equal volume, after regulating pH and be 4～5 with salt of weak acid solution, with volume-adjustment with aforementioned consistent, under 10～80 ℃, reacted 10～120 minutes, and obtained the sample of deriving;
3), among employing and the A 4)-5) identical step carries out efficient liquid phase chromatographic analysis to the sample of deriving;
4), the test result of samples of will deriving contrasts with glyoxal typical curve, glyoxalic acid typical curve and acetaldehyde typical curve respectively, try to achieve glyoxal in the sample solution, the content of glyoxalic acid and acetaldehyde.
Can prepare 5～7 concentration in the preferred above-mentioned glyoxal standard solution preparation and be the glyoxal standard solution between 0.1g/L～1g/L; Can prepare 5～7 concentration in the glyoxalic acid standard solution preparation and be the glyoxalic acid standard solution between 0.05g/L～0.5g/L; It is acetaldehyde standard solution between 10g/L～100g/L that the acetaldehyde standard solution can be prepared 5～7 concentration.
The mol ratio of preferred oxammonium hydrochloride of derivatization process and aldehyde radical is 2: 1～20: 1 in preferred above-mentioned A, B, C, the D step, under 20～60 ℃, reacts 25～60 minutes.
The pH of the deionized water of high performance liquid chromatography testing process preferred flow in mutually is 2.5～3 in above-mentioned A, B, C, the D step, adopts UV-detector.
The present invention also can test respectively separately glyoxal, glyoxalic acid, acetaldehyde, can analyze organic acids such as acetate in the acetaldehyde solution, oxalic acid, directly analyze during operation with liquid chromatography, need not the step that oxammonium hydrochloride is derived, other conditions with analyze glyoxal, the conditionally complete of glyoxalic acid, acetaldehyde is identical.
Beneficial effect:
The highly effective liquid phase chromatography detection method of glyoxal of the present invention, glyoxalic acid, acetaldehyde, be a kind of have easy to operate, automaticity is high, selectivity is high, detection is sensitive, the analytical approach of advantage quick and precisely, and can reach the purpose of measuring various ingredients simultaneously.Experimental result shows, highly effective liquid phase chromatography detection method detects oxidation of acetaldehyde generation glyoxal fast, accurately, simultaneously, during the composition of the liquor sample of gained (be glyoxal, the mixed liquor of glyoxalic acid, acetaldehyde, acetate, oxalic acid etc.), to product and reactant, especially the principal product glyoxal quantitative measurement obtained good effect, can the phase mutual interference between the mensuration of each component.Therefore, high performance liquid chromatography of the present invention not only can detect single species rapidly and sensitively, and, oxidation of acetaldehyde provides a kind of accurate detection method for preparing glyoxal technology, remedy the chemical analysis process of always prolonging usefulness loaded down with trivial details, can not detect, be subject to deficiencies such as interference simultaneously, the glyoxal technology of improvement and development prepare to(for) oxidation of acetaldehyde have realistic meaning.Relevant experimental result can further specify from following embodiment.
Description of drawings
Fig. 1-1,1-2 be respectively among the embodiment 1 with high performance liquid chromatography detect glyoxal that oxammonium hydrochloride derives liquid chromatogram and typical curve.
Fig. 2-1,2-2 are respectively the liquid chromatogram and the typical curve of the glyoxalic acid of deriving with high performance liquid chromatography detection oxammonium hydrochloride among the embodiment 2.
Fig. 3-1,3-2 are respectively the liquid chromatogram and the typical curve of the acetaldehyde of deriving with high performance liquid chromatography detection oxammonium hydrochloride among the embodiment 3.
Fig. 4 among the embodiment 4 with high performance liquid chromatography detect the glyoxal that oxammonium hydrochloride derives, the liquid chromatogram of glyoxalic acid and acetaldehyde mixed solution.
Fig. 5 among the embodiment 5 with high performance liquid chromatography detect oxidation of acetaldehyde that oxammonium hydrochloride derives prepare glyoxal the liquid chromatogram of glyoxal and glyoxalic acid in the reaction product sample.
Fig. 6-1,6-2 be respectively among the embodiment 6 with high performance liquid chromatography detect glyoxal that oxammonium hydrochloride derives liquid chromatogram and typical curve.
Fig. 7-1,7-2 are respectively the liquid chromatogram and the typical curve of the glyoxalic acid of deriving with high performance liquid chromatography detection oxammonium hydrochloride among the embodiment 7.
Fig. 8-1,8-2 are respectively the liquid chromatogram and the typical curve of the acetaldehyde of deriving with high performance liquid chromatography detection oxammonium hydrochloride among the embodiment 8.
Fig. 9 among the embodiment 9 with high performance liquid chromatography detect the glyoxal that oxammonium hydrochloride derives, the liquid chromatogram of glyoxalic acid and acetaldehyde mixed solution.
Embodiment
Following embodiment will the present invention is further illustrated in conjunction with the accompanying drawings.Not thereby limiting the invention.
Embodiment 1: the drafting of glyoxal typical curve
A), the preparation of glyoxal standard solution: get 40wt% glyoxal solution 1mL, in the 50mL volumetric flask, get the 10g/L glyoxal solution with the deionized water constant volume; Pipette 0.5,1.5,2,2.5,3.5,4.5 respectively from this solution, 5mL is in the 50mL volumetric flask, and constant volume gets 0.1,0.3,0.4,0.5,0.7,0.9,1g/L glyoxal standard solution;
B), the glyoxal system oxime compounds sample of deriving: get 0.1,0.3,0.4,0.5,0.7,0.9 respectively, 1.0g/L glyoxal standard solution 5mL, add 2g/L oxammonium hydrochloride solution 15mL, behind sodium acetate solution adjusting pH, with all samples volume-adjustment unanimity, under 40 ℃, reacted 30 minutes, and obtained the glyoxal oximate derivant of variable concentrations;
C), to adopt Agilent 1100 type high performance liquid chromatographs be analytical instrument, is furnished with the standard automatic sampler, variable wavelength scanning UV-detector (190nm～600nm) and Agilent chromatographic work station.Chromatographic condition is: ZORBAX Eclipse XDB-C
18Chromatographic column, the volume ratio of acetonitrile and water (pH is 3～4) is 10/90, and flow velocity is 1ml/min, and column temperature is 25 ℃, and sample size is 2 μ L, the detection wavelength is 220nm.Detect the glyoxal oximate derivant of variable concentrations successively, adopt the Agilent chem workstation that experimental data is carried out recording processing.The spectrogram of glyoxal oximate derivant (0.5g/L) is seen shown in Fig. 1-1.Horizontal ordinate is retention time/min among Fig. 1-1, ordinate is absorbance log/mAU, the clear glyoxal oximate derivant that shows has two spectrum peak a and b among the figure, and peak position is got fine, illustrates that glyoxal generates glyoxal monoxime and two kinds of derivants of glyoxal dioxime with the oxammonium hydrochloride reaction.Because this tests used high performance liquid chromatography is reversed phase partition chromatography, therefore consider that from molecular weight and polarity two aspects a (retention time 4.6min) is the peak of glyoxal monoxime, b (retention time 5.0min) is the peak of glyoxal dioxime.
D), the spectrogram of variable concentrations glyoxal oximate derivant relatively, find that the ratio of the glyoxal monoxime and the peak area of glyoxal dioxime keeps constant, therefore the peak area of available glyoxal monoxime is as quantitative basis drawing standard working curve, shown in Fig. 1-2.From Fig. 1-2 as seen, between the spectrum peak area A of the glyoxal monoxime that adopts glyoxal concentration C (g/L) that this method measures and its to derive to obtain, in 0.01～1g/L concentration range, show good linear relationship.Equation of linear regression is y=-11.414+2619.821x, linear regression coeffficient R=0.9999, glyoxal detection be limited to 0.00142g/L.
Embodiment 2: the drafting of glyoxalic acid typical curve:
A), the preparation of glyoxalic acid standard solution: take by weighing the 0.1g glyoxalic acid in the 100mL volumetric flask, get the 1g/L glyoxylic acid solution with the deionized water constant volume; Pipette 2.5,5,7.5,10,12.5,15 respectively from this solution, 17.5mL is in the 50mL volumetric flask, and constant volume gets 0.05,0.1,0.15,0.2,0.25,0.3,0.35g/L glyoxalic acid standard solution;
B), the glyoxalic acid system oxime compounds sample of deriving: get 0.05,0.1,0.15 respectively, 0.2,0.25,0.3,0.35g/L glyoxalic acid standard model solution 5mL, add 15mL2g/L oxammonium hydrochloride solution, after utilizing sodium acetate solution to regulate pH, with all samples volume-adjustment unanimity, under 40 ℃, reacted 30 minutes, and obtained the glyoxalic acid oximate derivant of variable concentrations.
C), under the chromatographic condition identical with embodiment 1, detect the glyoxalic acid oximate derivant of variable concentrations successively, adopt the Agilent chem workstation that experimental data is carried out recording processing.The spectrum peak of glyoxalic acid oximate derivant (0.1g/L) is shown in Fig. 2-1.Horizontal ordinate is retention time/min among Fig. 2-1, and ordinate is absorbance log/mAU.From Fig. 2-1 as can be known, glyoxalic acid oximate derivant has only a spectrum peak, and retention time is 4.0min, illustrates that the reaction of glyoxalic acid and oxammonium hydrochloride only generates a kind of derivant;
D), concentration is mapped, obtain the standard working curve of glyoxalic acid, shown in Fig. 2-2 with the response peak area of the glyoxalic acid oximate derivant of variable concentrations.Fig. 2-2 shows, between the spectrum peak area A of the glyoxylic acid oxime that adopts glyoxalic acid concentration C (g/L) that this method measures and its to derive to obtain, shows good linear relationship in 0.05～0.35g/L concentration range.Equation of linear regression is y=0.271+194.357x, linear regression coeffficient R=0.9995, and the detection of glyoxalic acid is limited to 0.0135g/L.
Embodiment 3: the drafting of acetaldehyde typical curve
A), the preparation of acetaldehyde standard solution: pipette 1.25,2.5,5,7.5 respectively, the 40wt% acetaldehyde solution of 10mL places the 50mL volumetric flask, and constant volume gets 10,20,40,60,80g/L acetaldehyde standard solution;
B), the acetaldehyde system oxime compounds sample of deriving: get 10 respectively, 20,40,60, the acetaldehyde standard solution 5mL of 80g/L, add 50g/L oxammonium hydrochloride solution 15mL, behind sodium acetate adjusting pH, with all samples volume-adjustment unanimity, under 40 ℃, reacted 30 minutes, and obtained the acetaldehyde oximate derivant of variable concentrations;
C), under the chromatographic condition identical with embodiment 1, detect the acetaldehyde oximate derivant of variable concentrations successively, adopt the Agilent chem workstation that experimental data is carried out recording processing.Acetaldehyde oximate derivant (60g/L) is shown in Fig. 3-1.Horizontal ordinate is retention time/min among Fig. 3-1, and ordinate is absorbance log/mAU.From Fig. 3-1 as can be known, acetaldehyde oximate derivant has only a spectrum peak, and retention time is 5.6min, illustrates that the reaction of acetaldehyde and oxammonium hydrochloride only generates a kind of derivant;
D), concentration is mapped, obtain the typical curve of acetaldehyde, shown in Fig. 3-2 with the response peak area of the acetaldehyde oximate derivant of variable concentrations.Fig. 3-2 shows, between the spectrum peak area A of the acetaldoxime that adopts acetaldehyde concentration C (g/L) that this method measures and its to derive to obtain, shows good linear relationship in 10～80g/L concentration range.Equation of linear regression is y=-3.354+6.194x, linear regression coeffficient R=0.9975, and the detection of acetaldehyde is limited to 1g/L.
Embodiment 4: preparation 0.1g/L glyoxal, the mixed solution of 0.1g/L glyoxalic acid and 20g/L acetaldehyde, get this mixed solution of 5ml, add 10g/L oxammonium hydrochloride solution 15mL, after utilizing sodium acetate solution to regulate pH, volume-adjustment is consistent to the drawing standard curve time, under 40 ℃, reacted 30 minutes.The liquid-phase chromatographic analysis result as shown in Figure 4.Horizontal ordinate is retention time/min among Fig. 4, and ordinate is absorbance log/mAU.As can be seen from Figure 4, at the retention time place of corresponding glyoxal monoxime and the two oximes of glyoxal, glyoxylic acid oxime, acetaldoxime four peak a appear, b, c, d, degree of separation is better, show this assay method to detect glyoxal, glyoxalic acid, acetaldehyde have good selectivity.With the peak area of glyoxal monoxime, glyoxylic acid oxime, acetaldoxime respectively for people's glyoxal typical curve regression equation, glyoxalic acid typical curve regression equation and acetaldehyde typical curve regression equation, glyoxal concentration 0.0999g/L, glyoxalic acid concentration are that 0.09997g/L, acetaldehyde concentration are 19.14g/L, testing result is almost consistent with the actual concentrations of preparation, show this assay method be used to detect glyoxal, the mixed solution of glyoxalic acid and acetaldehyde is accurately and reliably.
Embodiment 5: adopt this method to oxidation of acetaldehyde prepare glyoxal reaction product solution detect: get the 1mL oxidation of acetaldehyde prepare glyoxal reaction product solution, be settled to 100mL, promptly dilute 100 times, therefrom get the 5mL sample, add 2g/L oxammonium hydrochloride solution 15mL, regulate pH with sodium acetate solution after, volume-adjustment is consistent to the drawing standard curve time, under 40 ℃, reacted 30 minutes.Liquid chromatographic detection the results are shown in Figure 5.Horizontal ordinate is retention time/min among Fig. 5, and ordinate is absorbance log/mAU.From Fig. 5 as seen, at the retention time place of corresponding glyoxal monoxime and the two oximes of glyoxal, glyoxylic acid oxime three peak a appear, b, and c, and the degree of separation at peak is fine.In addition the spectrum peak that does not have other illustrates that the acetaldehyde concentration in solution this moment is lower than its detectability, and by-product acetic acid, oxalic acid do not disturb the detection of glyoxal and glyoxalic acid oximate derivant yet in addition.With the peak area of the peak area of glyoxal monoxime and glyoxylic acid oxime respectively for people's glyoxal standard working curve regression equation and glyoxalic acid standard working curve regression equation, obtain in the sample glyoxal concentration be that 0.543g/L, glyoxalic acid concentration are 0.103g/L, multiply by respectively 100 54.3g/L and 10.3g/L.
Embodiment 6: the drafting of glyoxal typical curve
A), the preparation of glyoxal standard solution is with a) step among the embodiment 1;
B), the glyoxal system oxime compounds sample of deriving: get 0.1,0.3,0.4,0.5,0.7,0.9 respectively, 1.0g/L glyoxal standard solution 10mL, add 5g/L oxammonium hydrochloride solution 20mL, behind sodium acetate solution adjusting pH, with all samples volume-adjustment unanimity, under 55 ℃, reacted 40 minutes, and obtained the glyoxal oximate derivant of variable concentrations;
C), adopting Agilent 1100 type high performance liquid chromatographs is analytical instrument.Chromatographic condition is: ZORBAXEclipse XDB-C
18Chromatographic column, the volume ratio of acetonitrile and water (pH is 3～4) is 25/75, and flow velocity is 1.2ml/min, and column temperature is 35 ℃, and sample size is 1 μ L, the detection wavelength is 250nm.Detect the glyoxal oximate derivant of variable concentrations successively, adopt the Agilent chem workstation that experimental data is carried out recording processing.The spectrogram of glyoxal oximate derivant (0.5g/L) is seen shown in Fig. 6-1.A among the figure (retention time 3.7min) is the peak of glyoxal monoxime, and b (retention time 4.1min) is the peak of glyoxal dioxime.
D), use the peak area of glyoxal monoxime as quantitative basis drawing standard working curve, shown in Fig. 6-2.From Fig. 6-2 as seen, glyoxal concentration C (g/L) and its are derived between the spectrum peak area A of the glyoxal monoxime that obtains, show good linear relationship in 0.01～1g/L concentration range.Equation of linear regression is y=0.964+2212.552x, linear regression coeffficient R=0.9996, glyoxal detection be limited to 0.00131g/L.
Embodiment 7: the drafting of glyoxalic acid typical curve:
A), the preparation of glyoxalic acid standard solution is with a) step among the embodiment 2;
B), the glyoxalic acid system oxime compounds sample of deriving: get 0.05,0.1,0.15 respectively, 0.2,0.25,0.3,0.35g/L glyoxalic acid standard model solution 10mL, add 20mL5g/L oxammonium hydrochloride solution, after utilizing sodium acetate solution to regulate pH, with all samples volume-adjustment unanimity, under 55 ℃, reacted 40 minutes, and obtained the glyoxalic acid oximate derivant of variable concentrations.
C), under the chromatographic condition identical with embodiment 6, detect the glyoxalic acid oximate derivant of variable concentrations successively, adopt the Agilent chem workstation that experimental data is carried out recording processing.The spectrum peak of glyoxalic acid oximate derivant (0.1g/L) is shown in Fig. 7-1, and retention time is 3.1min.
D), concentration is mapped, obtain the standard working curve of glyoxalic acid, shown in Fig. 7-2 with the response peak area of the glyoxalic acid oximate derivant of variable concentrations.Fig. 7-2 shows, glyoxalic acid concentration C (g/L) and its are derived between the spectrum peak area A of the glyoxylic acid oxime that obtains, show good linear relationship in 0.05～0.35g/L concentration range.Equation of linear regression is y=-0.886+157.286x, linear regression coeffficient R=0.9989, and the detection of glyoxalic acid is limited to 0.0101g/L.
Embodiment 8: the drafting of acetaldehyde typical curve
A), the preparation of acetaldehyde standard solution is with a) step among the embodiment 3;
B), the acetaldehyde system oxime compounds sample of deriving: get 10 respectively, 20,40,60, the acetaldehyde standard solution 10mL of 80g/L, add 100g/L oxammonium hydrochloride solution 20mL, behind sodium acetate adjusting pH, with all samples volume-adjustment unanimity, under 55 ℃, reacted 40 minutes, and obtained the acetaldehyde oximate derivant of variable concentrations;
C), under the chromatographic condition identical with embodiment 6, detect the acetaldehyde oximate derivant of variable concentrations successively, adopt the Agilent chem workstation that experimental data is carried out recording processing.Acetaldehyde oximate derivant (60g/L) is shown in Fig. 8-1, and retention time is 4.7min.
D), concentration is mapped, obtain the typical curve of acetaldehyde, shown in Fig. 8-2 with the response peak area of the acetaldehyde oximate derivant of variable concentrations.Fig. 8-2 shows, between the spectrum peak area A of the acetaldoxime that adopts acetaldehyde concentration C (g/L) that this method measures and its to derive to obtain, shows good linear relationship in 10～80g/L concentration range.Equation of linear regression is y=-1.818+5.125x, linear regression coeffficient R=0.9981, and the detection of acetaldehyde is limited to 0.985g/L.
Embodiment 9: with embodiment 4 preparation glyoxals, the mixed solution of glyoxalic acid, acetaldehyde, get this mixed solution of 10ml, add 20g/L oxammonium hydrochloride solution 20mL, after utilizing sodium acetate solution to regulate pH, volume-adjustment is consistent to the drawing standard curve time, under 55 ℃, reacted 40 minutes.The liquid-phase chromatographic analysis result as shown in Figure 9.As can be seen from Figure 9, at the retention time place of corresponding glyoxal monoxime and the two oximes of glyoxal, glyoxylic acid oxime, acetaldoxime four peak a appear, b, c, d, degree of separation is better, show this assay method to detect glyoxal, glyoxalic acid, acetaldehyde have good selectivity.With the peak area of glyoxal monoxime, glyoxylic acid oxime, acetaldoxime respectively for people's glyoxal typical curve regression equation, glyoxalic acid typical curve regression equation and acetaldehyde typical curve regression equation, glyoxal concentration 0.0994g/L, glyoxalic acid concentration are that 0.0998g/L, acetaldehyde concentration are 19.58g/L, testing result is almost consistent with the actual concentrations of preparation, show this assay method be used to detect glyoxal, the mixed solution of glyoxalic acid and acetaldehyde is accurately and reliably.
Claims (6)
- One kind detect glyoxal, high performance liquid chromatography (HPLC) method of glyoxalic acid, acetaldehyde, concrete steps are as follows:The drafting of A, glyoxal typical curve1), the preparation of glyoxal standard solution: get an amount of glyoxal solution with transfer pipet, respectively with the deionized water dilution, and constant volume, prepare the glyoxal standard solution of 5～7 concentration between 0.1g/L～2g/L;2), the preparation of derivative reagent: take by weighing the appropriate hydrochloric acid azanol, with deionized water dissolving prepare 1～10g/L oxammonium hydrochloride solution;3), glyoxal is derived and is produced the oximate sample: the above-mentioned glyoxal standard solution of getting equal volume, variable concentrations respectively, adding concentration respectively is 1～10g/L oxammonium hydrochloride solution, the mol ratio of oxammonium hydrochloride and aldehyde radical is 1.5: 1～50: 1, after regulating pH and be 4～5 with salt of weak acid solution, with all samples volume-adjustment unanimity, under 10～80 ℃, reacted 10～120 minutes, obtain glyoxal oximate derivant;4), preparation pH is 2～5 deionized water, with trifluoroacetic acid aqueous solution as efficient liquid phase chromatographic analysis moving phase;5), with efficient liquid phase chromatographic analysis above-mentioned steps 3) the glyoxal oximate derivant sample of the variable concentrations prepared, adopt UV-detector, chromatographic condition is:Chromatographic column: ZORBAX Eclipse XDB-C 18, 5 μ m, 4.6 * 250mm;Moving phase: the volume ratio of acetonitrile and water is 5/95～60/40;Flow velocity: 0.6～2ml/min;Column temperature: 20～50 ℃;Sample size: 1～20 μ L;Detect wavelength: 200～300nm;6), concentration is mapped, with the response peak area of the glyoxal oximate derivant of variable concentrations obtain glyoxal typical curve;The drafting of B, glyoxalic acid typical curve1), the preparation of glyoxalic acid standard solution: take by weighing the glyoxalic acid sample of different quality respectively, use deionized water dissolving, and constant volume, prepare 5～7 concentration and be the glyoxalic acid standard solution between 0.01g/L～1g/L.2), according in the steps A 2) preparation steps preparation oxammonium hydrochloride;3), glyoxalic acid is derived and is produced the oximate sample: get with steps A in 3) glyoxal standard solution volume identical, among the above-mentioned steps B 1) the glyoxalic acid standard solution of the variable concentrations of preparation, add with steps A in 3) oxammonium hydrochloride that volume is identical, after regulating pH and be 4～5 with salt of weak acid solution, with all samples volume-adjustment unanimity, under 10～80 ℃, reacted 10～120 minutes, obtain glyoxalic acid oximate derivant;4), among employing and the A 4)～6) same step draws the typical curve of glyoxalic acid;The drafting of C, acetaldehyde typical curve1), the preparation of acetaldehyde standard solution: pipette an amount of acetaldehyde solution with transfer pipet, respectively with the deionized water dilution, and constant volume, prepare the acetaldehyde standard solution of 5～7 concentration between 5g/L～100g/L;2), the preparation of derivative reagent: take by weighing oxammonium hydrochloride, with deionized water dissolving prepare 10～100g/L oxammonium hydrochloride solution;3), acetaldehyde is derived and is produced the oximate sample: get with steps A in 3) glyoxal standard solution volume identical, above-mentioned steps 1) in the above-mentioned acetaldehyde standard solution of variable concentrations of preparation, add with steps A in 3) 10～100g/L oxammonium hydrochloride that volume is identical, after regulating pH and be 4～5 with salt of weak acid solution, with all samples volume-adjustment unanimity, under 10～80 ℃, reacted 10～120 minutes, and obtained acetaldehyde oximate derivant;4), among employing and the A 4)-6) same step draws the typical curve of acetaldehyde;The deriving and detect of D, unknown concentration sample1), according in the steps A 2) preparation steps preparation oxammonium hydrochloride;2), get with steps A in 3) the glyoxal that contains unknown concentration that volume is identical, glyoxalic acid, acetaldehyde mixed solution, add with steps A in 3) oxammonium hydrochloride of equal volume, after regulating pH and be 4～5 with salt of weak acid solution, with volume-adjustment with aforementioned consistent, under 10～80 ℃, reacted 10～120 minutes, and obtained the sample of deriving;3), among employing and the A 4)-5) identical step carries out efficient liquid phase chromatographic analysis to the sample of deriving;4), the test result of samples of will deriving contrasts with glyoxal typical curve, glyoxalic acid typical curve and acetaldehyde typical curve respectively, try to achieve glyoxal in the sample solution, the content of glyoxalic acid and acetaldehyde.
- 2. the detection method described in claim 1 is characterized in that preparing the glyoxal standard solution of 5～7 concentration between 0.1g/L～1g/L.
- 3. the detection method described in claim 1 is characterized in that preparing the glyoxalic acid standard solution of 5～7 concentration between 0.05g/L～0.5g/L.
- 4. the detection method described in claim 1 is characterized in that preparing the acetaldehyde standard solution of 5～7 concentration between 10g/L～100g/L.
- 5. the detection method described in claim 1, the condition of producing the oximate sample that it is characterized in that deriving among steps A, B, C, the D is: the mol ratio of oxammonium hydrochloride and aldehyde radical is 2: 1～20: 1, under 20～60 ℃, reacts 25～60 minutes.
- 6. the detection method described in claim 1 is characterized in that steps A, 4) in be 2.5～3 as the pH of the deionized water of one of moving phase.
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