CN106018392B - A kind of novel vinegar vinegar age rapid detection method - Google Patents
A kind of novel vinegar vinegar age rapid detection method Download PDFInfo
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Abstract
The invention discloses a kind of novel vinegar vinegar age rapid detection methods, belong to the utilization of brewage raw material and field of quality control；The present invention passes through GC-MS first and analyzes feature escaping gas in different vinegar age vinegars, then it is filtered out by experimental method combination ultraviolet visible spectrometry to the quick material of color that characteristic gas is sensitive, color sensitive sensor array is made, the color sensitive sensor array of computer analysis is finally reacted to color change gray scale difference value input KNN (K nearest neighbor method) model of front and back with vinegar sample to differentiate the vinegar age of vinegar.The present invention detects its vinegar age by the feature escaping gas of the quick material tests difference vinegar age vinegar of color, it is a kind of quick, objective, low price method, the present invention is to having practical significance in terms of to meeting the needs of consumer is to food quality and safety and Maintenance Market order.
Description
Technical field
The present invention relates to a kind of rapid detection methods in novel vinegar vinegar age, refer in particular to a kind of based on color sensitive sensor technology
The Fast nondestructive evaluation Solid-state fermentation vinegar time limit method, belong to brewage field of quality control.
Background technique
Vinegar is the traditional fermented food in China, in addition to as a kind of daily flavouring, there are also important health care and is resisted
Cancer effect.Ageing has a decisive role the quality for improving vinegar, and a variety of volatile components in vinegar occur for ageing
Complicated variation, storage is more long, and taste is cured alcohol, and nutritive value also gets a promotion, and undergoes no deterioration.The vinegar age of vinegar refers to food
In the time of vinegar ageing, the vinegar of different years is since there are larger differences for mouthfeel effect.The more long vinegar of ageing, mouthfeel more preferably,
Beneficial agents are more, and price is corresponding also higher.Currently there are random mark vinegar vinegar age phenomenons, have both invaded consumer
Equity, also upset the order in market.At present the detection method in vinegar vinegar age mainly have sense organ rating method, gas chromatography,
Near-Infrared Absorption Method etc., however sensory evaluation needs the reviewer of professional training, and evaluation result is affected by subjective factor；By
Text " HS-SPME/GC-MS and chemometrics for the classification of Balsamic Vinegars
It is effective using gas chromatography result principal component analysis in of Modena of different maturation and ageing "
The ageing time of Italy's aromatic vinegar is distinguished, but the equipment of chromatogram analysis method is expensive and cumbersome time-consuming；Paper " is based on
Near infrared spectrum is quantitative to the pH value and soluble solid of mature vinegar to be studied with qualitatively detection " in using near-infrared to difference
East Lake mature vinegar of the time limit is distinguished, but these instruments are more expensive, cannot be widely used in real life.
Therefore a kind of method for finding easy quickly detection vinegar vinegar age, to meeting consumer to food quality and safety
It is had practical significance in terms of demand and Maintenance Market order.Color sensitive sensor technology is a kind of gas occurred in recent years
The new method of characterization reacts under test gas the color difference of front and back using color sensitive sensor, under test gas carry out it is qualitative and
Quantitative analysis.Patent " a kind of zhenjiang vinegar storage time discrimination method merged based on smell and taste sensor information " is open
A kind of zhenjiang vinegar storage time discrimination method based on Multi-sensor Fusion, but not to the vinegar marker of different years into
Row analysis, and the quick material of color chosen is the quick material of commercialized color, the quick material of these colors is usually spectrum (i.e. to a variety of
Gas sensitization), it is difficult to for certain in food Volatilized smell or a variety of special gas detection analyses for reflecting its qualitative characteristics.
Currently, the quick detection that the quick material of color is used for vinegar vinegar age marker is had not been reported.
Summary of the invention
It is an object of the invention to overcome the shortcomings of existing vinegar vinegar age detection method, propose a kind of based on the quick material skill of color
The detection method of the vinegar vinegar age marker of art, it is easy to operate, it is low in cost, as a result accurately and reliably.
The technical solution of the present invention is as follows: a kind of novel vinegar vinegar age rapid detection method, this method is to utilize the quick material of color
The vinegar odor response color difference from different vinegar ages is expected to differentiate the vinegar age of vinegar, is mainly included the following steps:
Step 1) determines the feature escaping gas of different vinegar age vinegars by GC-MS first, and detected feature is waved
Hair property gas using 2,3- diacetyl, 2,4,5- trimethyl oxazole, 2,3,5,6- Tetramethylpyrazine as the ageing time marker；
Step 2) measures porphyrin and metalloporphyrin containing active different metal ion by experimental method, volatilizees with feature
The reaction gray scale difference value of gas carries out primary dcreening operation, then by ultravioletvisible spectroscopy to the metalloporphyrin containing different substituents
Further progress sensitivity screening；The quick material sensors array of color is made；
Step 3) obtains the Initial R of reaction front sensor array, G, B image transmitting by camera to computer, computer
It carries out image procossing and obtains priming color information, acquire the vinegar escaping gas in different vinegar ages, the information of acquisition is transferred to
Computer carries out image procossing to obtain the eigenmatrix of different vinegar age vinegar escaping gas；
Step 4) is reacted using the quick material sensors array of color with sample escaping gas, extracts relevant information, input is
The detection to vinegar sample vinegar age to be measured can be realized in the K nearest neighbor method discrimination model for building up vinegar vinegar age.
Further, the detailed process of the step 1) are as follows:
Step 1.1,8mL aromatic vinegar sample is pipetted in the extraction flask of 15mL with pipette and 2.5g solid sodium chloride is added,
Screw lid；The effect that sodium chloride is wherein added is to promote the volatilization of escaping gas in aromatic vinegar, and extraction flask is then placed in 45
DEG C water bath with thermostatic control in heat, SPME extracting head is inserted into sample from the rubber pad of bottle cap by frequency of oscillation 250r/min
Fiber head, headspace absorption 40min are released in head space part；
Step 1.2, after extraction, SPME extracting head is extracted from extraction flask, then extracting head is inserted into the sample introduction of GC-MS instrument
Mouthful, release fiber head, retract fiber head after desorbing 3min at 250 DEG C and extract extracting head from injection port, complete sample into
Sample；Wherein, chromatographic condition: DB-WAX type chromatographic column 60m × 0.25mm × 0.25 μm, carrier gas He flow are 0.8mL/min, regardless of
Stream, injector temperature are 250 DEG C；Column temperature: 35 DEG C of initial temperature lasting 5min, with 5 DEG C/min be warming up to after 100 DEG C with 3 DEG C/
Min is warming up to 200 DEG C, is finally warming up to 220 DEG C with 10 DEG C/min, keeps 15min；Mass Spectrometry Conditions: interface temperature is 250 DEG C,
The temperature of ion source is 230 DEG C, ionizes mode EI+, electron energy 70eV, 33~450amu of range of scanning quality pass through
HP-Chemstation System work station acquires and handles data；
Step 1.3, volatile component in the aromatic vinegar of new vinegar and ageing 1-3 is detected to GC-MS instrument to analyze；From perfume (or spice)
It is detected altogether in vinegar in 46 kinds of volatile components, chooses 2,3- diacetyl, 2,4,5- trimethyl oxazoles, 2,3,5,6- tetramethyl pyrroles
Marker of the piperazine as the ageing time.
Further, the detailed process of the step 2) are as follows:
Porphyrin and containing active different metal ion manganese, zinc, iron, cobalt, copper, palladium metal metalloporphyrin complex is chosen, by it
It is dissolved in methylene chloride, concentration 2mg/mL is printed and dyed by point sample capillary and the quick biography of color is made on PVDF membrane
Then sensor takes 2,4, the 5- trimethyl oxazoles that 5mL concentration is 10mg/L molten with the original image of camera acquisition color sensitive sensor
Sensor is affixed on preservative film by liquid in beaker, by preservative film sealed beaker mouth, is immediately placed in 45 DEG C of baking ovens and is allowed sensor
With 2,4,5- trimethyl oxazole volatilization gas sufficiently react 20min, to take out sensor immediately after reaction and acquire reaction
The image of sensor afterwards；
1.2mg TPP, 1.4mg TPPZn, 1.5mg TPPZnF, 1.6mg TPPZnCl, 1.3mg TPPCl are weighed respectively
It is settled to 5mL with methylene chloride, then is finally diluted to 4 × 10 with methylene chloride-7Each porphyrin solution of mol/L is in the quartz of 1cm
In cuvette, be added the 1%2 of different volumes, 4,5- trimethyl oxazole solution, the solution different volumes be respectively as follows: 0uL, 20uL,
40uL,60uL,80uL,100uL,120uL,140uL；Absolute dichloromethane is purple with 100 type of Varian Cary as reference solution
It is special that outer spectrophotometer observes the ultraviolet-visible spectrum that each porphyrin compound is reacted with the 2,4,5- trimethyl oxazole of various concentration
Sign, and calculate the central metal ion ligancy and reaction bonded constant of complexation reaction；Pass through formulaThe central metal ion ligancy and reaction bonded constant for calculating complexation reaction, in formula, A1
For free porphyrin solution absorbance, A2 2,4, the porphyrin solution absorbance that 5- trimethyl oxazole is completely combined, A is difference 2,
Porphyrin absorbance under 4,5- trimethyl oxazole concentration, [C] are the concentration value of added 2,4,5- trimethyl oxazoles.
It further, further include that 2 kinds of porphyrins are filtered out by the above method is sensitive to these characteristic gas；Its
In, 2 kinds of porphyrins are CH3Porphyrins are dissolved in dichloromethane solvent, concentration by OTPP, TPPZnF respectively
It is 2mg/mL；2 kinds of quick materials of color are printed and dyed on PVDF membrane one by one by micro-sampling capillary, are made 2 kinds
This 2 kinds of color sensitive sensors are constituted the quick material sensors array of color by color sensitive sensor.
Further, in the step 4) K nearest neighbor method discrimination model foundation, concrete operations are by the quick material of color and vinegar
The RGB gray scale difference value data of escaping gas reaction front and back carry out principal component analysis, finally choose preceding 10 principal components building K most
Nearest neighbour method discrimination model differentiates vinegar age of vinegar.
Beneficial effects of the present invention:
1) present invention provides a kind of detection method in easy, stable, quick vinegar vinegar age.It is analyzed not by GC-MS
With the characteristic indication object of vinegar age vinegar, then the color sensitive to vinegar age marker is screened by experimental method and ultraviolet visible spectrometry
Quick material.
2) filtering out 2 kinds of porphyrins by experimental method and ultravioletvisible spectroscopy is CH3OTPP (is closed in laboratory
At), TPPZnF, porphyrins are dissolved in dichloromethane solvent respectively, concentration is 2mg/mL；PH indicator is bromine first
Phenol is green, is dissolved in ethyl alcohol, concentration 2mg/mL, and 3 kinds of quick materials of color are printed and dyed one by one by micro-sampling capillary and are gathering inclined two
On vinyl fluoride (PVDF) film, the quick material sensors array of color is made；The color sensitive sensor array filtered out by this method, can
Targetedly analyze the marker in vinegar vinegar age.Compared with artificial sense organ, the present invention is more objective, accurate；It is detected with instrument
Method compares, and the present invention is more convenient, and low in cost；Compared with the color sensitive sensor method of wide spectrum, the present invention is had more
Specificity and sensitivity, and provide a kind of pair of quick material screening methodologies of the sensitive color of characteristic gas.The present invention consumes satisfaction
It is had practical significance in terms of demand and Maintenance Market order of the person to food quality and safety.
Detailed description of the invention
Invention is further described in detail with reference to the accompanying drawings and detailed description；
Fig. 1 is a kind of novel vinegar vinegar age detection method schematic diagram；
Fig. 2 is vinegar age marker trend chart in zhenjiang vinegar；
Fig. 3 is the ultraviolet spectra and dynamics calculation figure of the 2,4,5- trimethyl oxazole effect of TPPZn and various concentration；
Wherein, (a) is the 2 of TPPZn and various concentration, the spectrogram of 4,5- trimethyl oxazoles effect；(b) be TPPZn with
The double reciprocal plot of the 2,4,5- trimethyl oxazole effect of various concentration；
Fig. 4 is KNN Model checking result figure.
Specific embodiment
The flow chart of method of the invention as shown in Figure 1, under will in conjunction with each embodiment shown in the drawings to the present invention into
Row detailed description.
Step 1: different vinegar the screening analysis of aromatic vinegar (by taking zhenjiang vinegar as an example) vinegar age marker: being determined by GC-MS first
The feature escaping gas of age vinegar.Include the following steps:
(1.1) 8mL aromatic vinegar sample is pipetted in the extraction flask of 15mL with pipette and 2.5g solid sodium chloride is added, screw
Lid.The effect that sodium chloride is wherein added is to promote the volatilization of escaping gas in aromatic vinegar.Then extraction flask is placed in 45 DEG C
It is heated in water bath with thermostatic control, frequency of oscillation 250r/min.SPME extracting head is inserted into the head space of sample from the rubber pad of bottle cap
Fiber head, headspace absorption 40min are released in part.
(1.2) after extracting, SPME extracting head is extracted from extraction flask, then extracting head is inserted into the injection port of GC-MS instrument,
Fiber head is released, fiber head is retracted after desorption 3min at 250 DEG C and extracts extracting head from injection port, complete the sample introduction of sample.
Wherein, chromatographic condition: DB-WAX type chromatographic column (60m × 0.25mm × 0.25 μm), carrier gas He flow are 0.8mL/min, regardless of
Stream, injector temperature are 250 DEG C.Column temperature: 35 DEG C of initial temperature lasting 5min, with 5 DEG C/min be warming up to after 100 DEG C with 3 DEG C/
Min is warming up to 200 DEG C, is finally warming up to 220 DEG C with 10 DEG C/min, keeps 15min；Mass Spectrometry Conditions: interface temperature is 250 DEG C,
The temperature of ion source is 230 DEG C, ionizes mode EI+, electron energy 70eV, 33~450amu of range of scanning quality.Pass through
HP-Chemstation System work station acquires and handles data.
(1.3) volatile component in the zhenjiang vinegar of new vinegar and ageing 1-3 is detected to GC-MS instrument to analyze and research.
As a result as shown in Fig. 2, finding 2,3- diacetyl, 2 in 46 kinds of volatile components from detecting altogether in aromatic vinegar, 4,5- trimethyls are disliked
Azoles and these three substances of Tetramethylpyradine content in new vinegar are few, but with the increase of ageing time, content
It obviously increases.For the vinegar of ageing 3 years compared with new vinegar, 2,3- diacetyl increase 3 times；2,4,5- trimethyl oxazole increases 36
Times；2,3,5,6- Tetramethylpyrazine increases 7 times.Illustrate that these three substances are mainly derived from traditional aging process, is the ageing time
Marker can be used as the important reference of zhenjiang vinegar vinegar age identification.
Step 2: the screening of the quick material of zhenjiang vinegar vinegar age marker sensitivity color；Porphyrin is measured by experimental method and containing work
Property different metal ion metalloporphyrin carry out primary dcreening operation with the gray scale difference value that reacts of feature volatilization gas, then by it is ultraviolet-
Vis spectroscopy screens the metalloporphyrin further progress sensitivity containing different substituents；The quick material sensors battle array of color is made
Column.
Specifically comprise the following steps:
(2.1) by the screening of the quick material of experimental method sensitivity color: choose porphyrin and containing active different metal ion manganese,
The Metalloporphyrins such as zinc, iron, cobalt, copper, palladium are dissolved in methylene chloride, and concentration 2mg/mL will by point sample capillary
Color sensitive sensor is made on polyvinylidene fluoride (PVDF) film in its printing and dyeing, and the original image of color sensitive sensor is acquired with camera,
Then it takes 2,4, the 5- trimethyl oxazole solution that 5mL concentration is 10mg/L in beaker, sensor is affixed on preservative film, will be protected
Fresh film sealed beaker mouth, is immediately placed in 45 DEG C of baking ovens and allows sensor and 2, and 4,5- trimethyl oxazole volatilization gas sufficiently react
20min, the image of sensor after taking out sensor immediately after reaction and acquiring reaction.
(2.2) pass through the screening of the quick material of ultraviolet visible spectrometry sensitivity color: weighing 1.2mg TPP, 1.4mg respectively
TPPZn, 1.5mg TPPZnF, 1.6mg TPPZnCl, 1.3mg TPPCl are settled to 5mL with methylene chloride, then use methylene chloride
Finally it is diluted to 4 × 10-7Each porphyrin solution of mol/L in the quartz colorimetric utensil of 1cm, be added different volumes (0uL, 20uL,
40uL, 60uL, 80uL, 100uL, 120uL, 140uL) 1%2,4,5- trimethyl oxazole solution, it is molten that absolute dichloromethane makees reference
Liquid observes 2,4,5- trimethyls of each porphyrin compound and various concentration with 100 type ultraviolet specrophotometer of Varian Cary
Oxazole reaction Ultraviolet-visible Spectroscopic Characteristics, and calculate complexation reaction central metal ion ligancy and reaction bonded it is normal
Number.Ligancy and binding constant can be acquired by the following formula: according to the variation of absorbance under certain wavelength, by lg ((A-A1)/
(A2- A)) the ligancy n of 2,4,5- trimethyl oxazoles and porphyrin can be acquired to the obtained slope of curve of lg [C] mapping, and by cutting
Away from binding constant K can be acquired.
(2.3) 2 kinds of porphyrins are filtered out by the above method and a kind of pH indicator is quick to these characteristic gas
Sense；Wherein, 2 kinds of porphyrins are CH3Porphyrins are dissolved in two by OTPP (laboratory synthesis), TPPZnF respectively
In chloromethane alkane solvents, concentration is 2mg/mL；PH indicator is bromocresol green, is dissolved in ethyl alcohol, concentration 2mg/mL；It is logical
It crosses micro-sampling capillary 3 kinds of quick materials of color are printed and dyed one by one on polyvinylidene fluoride (PVDF) film, 3 kinds of quick sensings of color is made
This 3 kinds of color sensitive sensors are constituted the quick material sensors array of color by device.
TPPZnF and 2, shown in ultraviolet-visible absorption spectroscopy such as Fig. 3 (a) of 4,5- trimethyl oxazoles effect, TPPZnF is two
Maximum absorption peak in chloromethanes solution is at 418nm, with the increase of 2,4,5- trimethyl oxazole concentration, maximum absorption peak
Final red shift 1nm, absorbance increases with concentration and reduces (Δ A=0.075), as can be seen from Fig. between 420nm-430nm
There is an apparent isoabsorptive point, illustrates that TPPZnF and 2,4,5- trimethyl oxazoles form the complex of 1:1.Fig. 3 (b) is root
Lg ((A-A1)/(A2-A)) is made to double inverse relationships of lg [C] by equation (1) according to langbobier law.It is related
Coefficient is 0.9982, slope 1, it was confirmed that TPPZnF with the effect of trimethyl oxazole is cooperated by 1:1.The intercept of equation is
0.4909 goes logarithm to obtain the binding constant K=3.10M-1 of TPPZnF Yu trimethyl oxazole.TPPZnF is in conjunction with trimethyl oxazole
So that the cloud density of its porphyrin ring is increased to energy required for reducing electron transition afterwards, makes the absorption band of porphyrin ring
Red shift.TPPZnF has preferable response to 2,4,5- trimethyl oxazoles, suitable for detecting to it.
The sample standard deviation of embodiment is provided by Zhenjiang perseverance along Cu Ye limited liability company in the step, totally 5 kinds of aromatic vinegar vinegar ages,
Including new vinegar and ageing 1 year, 2 years, 4 years aromatic vinegars, 30 samples of every kind of vinegar age, totally 120 samples；
From 24 kinds of quick materials of color (including metalloporphyrin manganese and derivative, metalloporphyrin iron and its derivative in 18 kinds of porphyrins,
Metalloporphyrin cobalt, metalloporphyrin copper, metalloporphyrin palladium, porphines and its derivative and ternary Porphyrin and its derivative), discovery
CH3The Δ R and Δ B value that O-TPP (methoxyl group porphyrin) and different vinegar age aromatic vinegars react have apparent difference, can be used as identification
The quick material of the feature in vinegar age.In addition, discovery bromocresol green is to vinegar with stronger in the acid-base indicator of 6 kinds of different pKa values
Response signal, RGB difference is maximum, and color change with the naked eye bright can be told.But bromocresol green imitates the identification in vinegar age
Fruit is bad.Its reason may be that bromocresol green has stronger sensibility to acid, but the acid substance in vinegar is not the marker in vinegar age.
Bromocresol green identifies contribution less to vinegar age, but one of the quick material of color that can be used as sensor, identifies vinegar age.
By the 3 kind porphyrins (CHs sensitive to zhenjiang vinegar vinegar age marker3OTPP, TPPZnF) it is dissolved in dichloromethane
Alkane, and a kind of pH indicator (bromocresol green) is dissolved in ethyl alcohol, concentration is 2mg/mL, is printed and dyed by point sample capillary
On polyvinylidene fluoride (PVDF) film, the interaction sensitization array sensor of 2 × 2 (2 rows 2 column) is made；
Step 3: the Initial R for reacting front sensor array, G, B image transmitting are obtained to computer, computer by camera
It carries out image procossing and obtains priming color information, acquire the vinegar escaping gas in different vinegar ages, the information of acquisition is transferred to
Computer carries out image procossing to obtain the eigenmatrix of different vinegar age vinegar escaping gas.
It accurately pipettes 10mL zhenjiang vinegar vinegar sample with pipette to be placed in a beaker, by sensor array silica gel plate rubber
Double-sided adhesive is fixed on preservative film, and by preservative film sealed beaker mouth, is exposed to sensor in aromatic vinegar escaping gas environment
It is reacted in 45 DEG C of baking oven.It is reacted after sensor with vinegar escaping gas and takes out visualized array biography after 18min reaches balance
Sensor, and with camera immediately obtain reaction after image.
Step 4: being reacted using the quick material sensors array of color with sample escaping gas, extract relevant information, input is
The detection to vinegar sample vinegar age to be measured can be realized in the K nearest neighbor method discrimination model for building up vinegar vinegar age.
The foundation of K nearest neighbor method (KNN) discrimination model in the step, concrete operations are by the quick material of color and vinegar volatility
RGB gray scale difference value data before and after gas reaction carry out principal component analysis, finally choose preceding 10 principal components and construct K nearest neighbor method
Discrimination model differentiates vinegar age of vinegar.
It is right using 80 independent samples (new vinegar, 1 year, 2 years, 4 years four classes of zhenjiang vinegar, each classification have 20 samples)
This method is verified, each sample totally 12 variables (quick material × 3 color component of 4 kinds of colors), as a result as shown in figure 4, knot
Fruit shows that this method reaches 90% to the synthesis discrimination of forecast set, shows that this method can be to rapidly and accurately detection vinegar
Vinegar age.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " illustrative examples ",
The description of " example ", " specific example " or " some examples " etc. means specific features described in conjunction with this embodiment or example, knot
Structure, material or feature are included at least one embodiment or example of the invention.In the present specification, to above-mentioned term
Schematic representation may not refer to the same embodiment or example.Moreover, specific features, structure, material or the spy of description
Point can be combined in any suitable manner in any one or more of the embodiments or examples.
Although an embodiment of the present invention has been shown and described, it will be understood by those skilled in the art that: not
A variety of change, modification, replacement and modification can be carried out to these embodiments in the case where being detached from the principle of the present invention and objective, this
The range of invention is defined by the claims and their equivalents.
Claims (3)
1. a kind of novel vinegar vinegar age rapid detection method, which is characterized in that this method is to utilize the quick material of color and different vinegar
The vinegar odor response color difference in age differentiates vinegar age of vinegar, mainly includes the following steps:
Step 1) determines the feature escaping gas of different vinegar age vinegars, detected feature volatility by GC-MS first
Gas using 2,3- diacetyl, 2,4,5- trimethyl oxazole, 2,3,5,6- Tetramethylpyrazine as the ageing time marker；
Step 2) measures porphyrin and metalloporphyrin containing active different metal ion by experimental method, with feature volatilization gas
Reaction gray scale difference value carry out primary dcreening operation, then by ultravioletvisible spectroscopy to the metalloporphyrin containing different substituents into one
The screening of stepping line sensitivity, is made the quick material sensors array of color；
Step 2) the detailed process are as follows:
It chooses porphyrin and containing active different metal ion manganese, zinc, iron, cobalt, copper, palladium metal metalloporphyrin complex, is dissolved in
Methylene chloride, concentration 2mg/mL are printed and dyed by point sample capillary and color sensitive sensor are made on PVDF membrane,
With camera acquisition color sensitive sensor original image, then take 5mL concentration be 10mg/L 2,4,5- trimethyl oxazole solution in
In beaker, sensor is affixed on preservative film, by preservative film sealed beaker mouth, is immediately placed in 45 DEG C of baking ovens and allows sensor and 2,
4,5- trimethyl oxazole volatilization gas sufficiently react 20min, pass after taking out sensor immediately after reaction and acquiring reaction
The image of sensor；
1.2mg TPP, 1.4mg TPPZn, 1.5mg TPPZnF, 1.6mg TPPZnCl, 1.3mg TPPCl are weighed respectively with two
Chloromethanes is settled to 5mL, then is finally diluted to 4 × 10 with methylene chloride-7Each porphyrin solution of mol/L is in the quartz cuvette of 1cm
In ware, be added the 1%2 of different volumes, 4,5- trimethyl oxazole solution, the solution different volumes be respectively as follows: 0uL, 20uL,
40uL,60uL,80uL,100uL,120uL,140uL；Absolute dichloromethane is purple with 100 type of Varian Cary as reference solution
It is special that outer spectrophotometer observes the ultraviolet-visible spectrum that each porphyrin compound is reacted with the 2,4,5- trimethyl oxazole of various concentration
Sign, and calculate the central metal ion ligancy and reaction bonded constant of complexation reaction；Pass through formulaThe central metal ion ligancy and reaction bonded constant for calculating complexation reaction, in formula, A1
For free porphyrin solution absorbance, A2It is the porphyrin solution absorbance that 2,4,5- trimethyl oxazoles are completely combined, A is difference 2,
Porphyrin absorbance under 4,5- trimethyl oxazole concentration, [C] are the concentration value of added 2,4,5- trimethyl oxazoles；
It is sensitive to these characteristic gas that 2 kinds of porphyrins are filtered out by the above method；Wherein, 2 kinds of porphyrins
For CH3Porphyrins are dissolved in dichloromethane solvent by OTPP, TPPZnF respectively, and concentration is 2mg/mL；By micro
Point sample capillary prints and dyes 2 kinds of quick materials of color on PVDF membrane one by one, 2 kinds of color sensitive sensors is made, by this 2 kinds of colors
Dependent sensor constitutes the quick material sensors array of color；
Step 3) obtains the Initial R of reaction front sensor array, G, B image transmitting by camera to computer, and computer carries out
Image procossing obtains priming color information, acquires the vinegar escaping gas in different vinegar ages, the information of acquisition is transferred to calculating
Machine carries out image procossing to obtain the eigenmatrix of different vinegar age vinegar escaping gas；
Step 4) is reacted using the quick material sensors array of color with sample escaping gas, and relevant information is extracted, and input has been built up
The detection to vinegar sample vinegar age to be measured can be realized in the K nearest neighbor method discrimination model in vinegar vinegar age.
2. novel vinegar vinegar age rapid detection method according to claim 1, which is characterized in that the tool of the step 1)
Body process are as follows:
Step 1.1,8mL aromatic vinegar sample is pipetted in the extraction flask of 15mL with pipette and 2.5g solid sodium chloride is added, screw
Lid；The effect that sodium chloride is wherein added is to promote the volatilization of escaping gas in aromatic vinegar, and extraction flask is then placed in 45 DEG C
It is heated in water bath with thermostatic control, SPME extracting head is inserted into the head space of sample by frequency of oscillation 250r/min from the rubber pad of bottle cap
Fiber head, headspace absorption 40min are released in part；
Step 1.2, after extraction, SPME extracting head is extracted from extraction flask, then extracting head is inserted into the injection port of GC-MS instrument,
Fiber head is released, fiber head is retracted after desorption 3min at 250 DEG C and extracts extracting head from injection port, complete the sample introduction of sample；
Wherein, chromatographic condition: DB-WAX type chromatographic column 60m × 0.25mm × 0.25 μm, carrier gas He flow are 0.8mL/min, are not shunted,
Injector temperature is 250 DEG C；Column temperature: 35 DEG C of initial temperature lasting 5min are warming up to after 100 DEG C with 5 DEG C/min with 3 DEG C/min liter
Temperature is finally warming up to 220 DEG C to 200 DEG C with 10 DEG C/min, keeps 15min；Mass Spectrometry Conditions: interface temperature is 250 DEG C, ion source
Temperature be 230 DEG C, ionize mode EI+, electron energy 70eV, 33~450amu of range of scanning quality pass through HP-
Chemstation System work station acquires and handles data；
Step 1.3, volatile component in the aromatic vinegar of new vinegar and ageing 1-3 is detected to GC-MS instrument to analyze；From aromatic vinegar
It is detected in 46 kinds of volatile components altogether, choose 2,3- diacetyl, 2,4,5- trimethyl oxazoles, Tetramethylpyradine are made
For the marker of ageing time.
3. novel vinegar vinegar age rapid detection method according to claim 1, which is characterized in that K in the step 4)
The foundation of nearest neighbor method discrimination model, concrete operations are that the quick material of color is reacted to the RGB gray scale of front and back with vinegar escaping gas
Difference data carries out principal component analysis, chooses preceding 10 principal components building K nearest neighbor method discrimination model finally to differentiate vinegar
Vinegar age.
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| CN110118747A (en) * | 2019-04-29 | 2019-08-13 | 山西农业大学 | The construction method of the decaying total reflection fourier-transform infrared finger-print of four big vinegar and application |
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