CN108226086A - A kind of red wine alcoholic strength and total sugar content quantitative analysis method - Google Patents
A kind of red wine alcoholic strength and total sugar content quantitative analysis method Download PDFInfo
- Publication number
- CN108226086A CN108226086A CN201810057312.4A CN201810057312A CN108226086A CN 108226086 A CN108226086 A CN 108226086A CN 201810057312 A CN201810057312 A CN 201810057312A CN 108226086 A CN108226086 A CN 108226086A
- Authority
- CN
- China
- Prior art keywords
- red wine
- sugar content
- total sugar
- alcoholic strength
- steps
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 230000001476 alcoholic effect Effects 0.000 title claims abstract description 97
- 235000020095 red wine Nutrition 0.000 title claims abstract description 95
- 238000000034 method Methods 0.000 title claims abstract description 94
- 238000004445 quantitative analysis Methods 0.000 title claims abstract description 27
- 238000001228 spectrum Methods 0.000 claims abstract description 27
- 238000012360 testing method Methods 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 238000002329 infrared spectrum Methods 0.000 claims description 20
- 238000004458 analytical method Methods 0.000 claims description 19
- 238000007689 inspection Methods 0.000 claims description 14
- 238000005516 engineering process Methods 0.000 claims description 12
- 230000003595 spectral effect Effects 0.000 claims description 6
- 238000004483 ATR-FTIR spectroscopy Methods 0.000 claims description 5
- 238000009499 grossing Methods 0.000 claims description 5
- 230000009466 transformation Effects 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 2
- 238000010832 independent-sample T-test Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000005259 measurement Methods 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 8
- 235000013305 food Nutrition 0.000 abstract description 2
- 235000014101 wine Nutrition 0.000 description 20
- 241000219095 Vitis Species 0.000 description 8
- 235000009754 Vitis X bourquina Nutrition 0.000 description 8
- 235000012333 Vitis X labruscana Nutrition 0.000 description 8
- 235000014787 Vitis vinifera Nutrition 0.000 description 8
- 238000009826 distribution Methods 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000012795 verification Methods 0.000 description 6
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000000692 Student's t-test Methods 0.000 description 3
- 244000269722 Thea sinensis Species 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 235000009508 confectionery Nutrition 0.000 description 3
- 238000007405 data analysis Methods 0.000 description 3
- 238000007427 paired t-test Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000007619 statistical method Methods 0.000 description 3
- 241001269238 Data Species 0.000 description 2
- 238000002512 chemotherapy Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 238000004497 NIR spectroscopy Methods 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 238000005102 attenuated total reflection Methods 0.000 description 1
- 238000009412 basement excavation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000013523 data management Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000004476 mid-IR spectroscopy Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000012163 sequencing technique Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3577—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing liquids, e.g. polluted water
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N2021/3595—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using FTIR
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2201/00—Features of devices classified in G01N21/00
- G01N2201/12—Circuits of general importance; Signal processing
- G01N2201/129—Using chemometrical methods
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
Abstract
The present invention provides a kind of red wine alcoholic strength and total sugar content quantitative analysis method.It is related to food Quantitative detection field, the method for the especially quick alcoholic strength and total sugar content for measuring red wine simultaneously.Specifically a kind of red wine alcoholic strength and total sugar content quantitative analysis method, including following key step：S100：The spectrum of the tested red wine of acquisition；S200：Decayed using single-point ATR and be totally reflected test pattern；S600：The alcoholic strength and total sugar content for obtaining the tested red wine quantify.
Description
Technical field
The invention belongs to field of rapid food detection, especially quickly measure the alcoholic strength of red wine simultaneously and total reducing sugar contains
The method of amount
Background technology
The alcoholic strength of domestic existing detection red wine and the method for total sugar content are mainly density bottle method, gas-chromatography
Method, alcohol meter method, direct titrimetric method.These methods more take, are laborious, and two kinds of contents cannot detect simultaneously.And in recent years
The quantitative analysis method of common grape wine physical and chemical composition is mostly near infrared spectroscopy, though compared to other methods, the method has letter
The advantages such as just, quick, lossless, but near-infrared spectrum technique, absorption signal is weaker, bands of a spectrum are more and overlapped, and information parsing is tired
Difficulty, in practical applications with certain limitation.Therefore, how to solve to the red wine of different alcohol and total sugar content
Quick detection, and can determine that its content is still the industry and is badly in need of the technical task solved.
Chinese Patent Application No. proposes a kind of " using Fourier Transform Near Infrared skill for CN201610223963.7
Art is to the detection method of five indices in grape wine " disclosure of the invention it is a kind of can simultaneously and quickly in measure grape wine five refer to
Object detection method includes the following steps：First, it will need to be measured in the wine samples cuvette detected；2nd, Fourier is opened
The workflow of transform near infrared spectrum instrument, acquisition need the spectrogram of wine samples detected, the instrument condition of spectra collection
Including：Acquisition technique is intelligence transmission accessory module, and scanning times are 16 times, and data format is absorptance, and background frequency is every
Hour, sampling technique is preceding sample room, and pre-acquired postpones 0 second, and attenuator is decayed (B Screen) for Type B, resolution ratio 8.0/
Cm, gain 8%, standard spectrum ranging from 4000/cm~10000/cm, background specification for position in rear sample room, background is swept
It is 16 times to retouch number；3rd, it using external standard method, is measured to obtain the Portugal for needing to detect with the Quantitative Analysis Model of standard glucose wine sample
The alcoholic strength of grape wine sample, total reducing sugar, reduced sugar, total acid, sugar-free extract content.
Invention content
In order to solve the problems, such as that two kinds of contents of the alcoholic strength of above-mentioned detection red wine and total sugar content detect simultaneously, this hair
It is bright to be achieved through the following technical solutions：
A kind of method of the quick alcoholic strength and total sugar content for measuring red wine simultaneously, specifically includes following six operation
Step：
(1) red wine sample is collected；
(2) alcoholic strength and total sugar content of national standard method determination sample are utilized；
(3) ir data of sample is acquired；
(4) it is the ir data of each sample is related to alcoholic strength and total sugar content the value one-to-one correspondence measured
Connection, is fitted using chemo metric software, establishes quantitative model；
(5) verification of quantitative model；
(6) measure of the alcoholic strength of unknown red wine sample and total reducing sugar
The domestic different alcoholic strengths of different manufacturers and the red wine of total sugar content are collected by step (1).
The alcoholic strength of wine sample, GB/T 15038-2006 are measured using GB/T 15038-2006 alcohol meters method by step (2)
Direct titrimetric method measures total sugar content.
When carrying out the acquisition of infrared spectrum by step (3), Britain platinum Ai Ermo Spotlight 400 are utilized
(PerkinElmer Spotlight 400) Fourier transformation infrared spectrometer (subsidiary PerkinElmer Universal ATR
Sample attachment), alternatively, match silent winged Buddhist nun's high-tensile strength iS5 (Thermo Scientific Nicolet iS5) Fourier transform in the U.S.'s is red
External spectrum instrument (subsidiary DTGS detectors and iD5 single-points ATR transmissions attachment), acquires the red wine of different wine types respectively
Infrared spectrum, dry type red wine are denoted as GX1, GX2 ..., and half-dry type is denoted as BG1, BG2 ..., and semi-sweet is denoted as BT1,
BT2 ..., sweet tea type are denoted as TX1, TX2 ...；
Decayed using single-point ATR and be totally reflected, (it is saturating that infrared spectrum sample analysis technology can be divided into Reflection to test pattern
It penetrates and reflects both of which with Transmission.Wherein attenuation total reflection (Attenuated Total Reflection, ATR)
For one kind of reflective-mode, principle is：During light wave incidence, the single color plane light wave of incident in-plane polarization is on the boundary of close-thin medium
During upper total reflection, evanescent field (see decaying wave) amount formed in optically thinner medium can be coupled to the surface of metal or semiconductor
Above make surface phasmon (SP) or Surface polaritons resonant excitation.Showing for acute remote attenuation thus occurs for the light intensity of total reflection
As.This pattern need not destroy sample, and directly sample is identified, substantially increase inspection speed；This method is easy to operate, surveys
High sensitivity is measured, can obtain the infrared spectrum of high quality.), scanning range 4000-400cm-1, scanning signal adds up 16 times, differentiates
Rate is ± 4cm-1, and obtain second dervative spectrogram using 9 multinomial least square methods are smooth.
PLS (Partial Least Squares) quantitative model is established using 9.0 analysis softwares of TQ Analyst according to step (4), is built
Before vertical calibration model, wavelength, number of principal components and Pretreated spectra need to be selected.
According to 4, the red wine sample of selection known alcohol degree and total sugar content in step (5), (content need to be in straightening die
Within type content range) as external certificate sample.Spectral scan is carried out by the infrared spectrum acquisition parameter in step (3), often
A sample parallel sweep 6 times.4 sample spectras are imported in the calibration model of alcoholic strengths and total sugar content, obtain alcoholic strength and
The predicted value of total sugar content.The measured value of infrared predicted value and alcohol meter method or direct titrimetric method is subjected to paired t-test, when setting
When fixation reliability is 95%, measured value that the predicted value that is obtained using the method for the present invention is obtained with alcohol meter method or direct titrimetric method
Between difference it is not notable.
This explanation using ATR-FTIR of the present invention (attenuation total reflection-FTIR spectrum), (be all-trans method by attenuation
Penetrate-FTIR spectrum technology (attenuated total reflectance-Fourier transform infrared
Spectroscopy, ATR-FTIR) spectral fingerprint feature in sample can be quickly detected, reflect that the molecular vibration in entire cell is special
Sign) measure red wine alcoholic strength and total sugar content be feasible.
According to the red wine sample that alcoholic strength and total sugar content to be measured are taken in step (6), according to the single-point in step (3)
ATR-FTIR methods acquisition parameter carries out IR spectrum scanning.Spectrum is directed respectively into alcoholic strength and total sugar content quantitative model,
The analysis result of alcoholic strength and total sugar content can quickly be obtained.
It should be noted that the present invention be suitable for red wine alcoholic strength content 7.7%vol~15.2%vol it
Between, total sugar content is between 1.75g/L~66.96g/L.Contain with the alcoholic strength and total reducing sugar of common domestic red wine on the market
Amount range is consistent.
Gained modeling result is that the related coefficient of alcoholic strength calibration set is 0.9672, calibration set root-mean-square error (RMSEC)
It is 0.341 to be worth, and the related coefficient for verifying collection is 0.9505, and forecast set root-mean-square error (RMSEP) value is 0.415；Total reducing sugar corrects
The related coefficient of collection is 0.9990, and calibration set root-mean-square error (RMSEC) value is 0.935, and the related coefficient for verifying collection is
0.9991, forecast set root-mean-square error (RMSEP) value is 0.972.T, which is examined, is also known as student t inspections (Student's t
test)：For testing model applicability, (sample is labeled as by sample of the red wine of different alcoholic strengths and total sugar content respectively
A, B, C, D) it is tested, each sample measures six times.
Acquired results look into t distribution tables：During f=n1+n2-2=10, if α=0.05, t10 0.05=1.812.tA、tB、tC、
TD values are respectively less than t10 0.05, i.e., in infrared analysis A, B, C, D samples between the predicted value and actual value of alcoholic strength and total sugar content not
There are significant differences, and when carrying out t inspections, it is in inspection level to look into t distribution tables:α=0.05, confidence level 95%, degree of freedom f
When being 10, the numerical value that is checked in.Show the red wine alcoholic strength built based on PLS methods and total sugar content respectively in 7.7-
The Quantitative Prediction Model of 15.2%vol, 1.75-66.96g/L work well, accurately can quickly measure red wine alcoholic strength and
Total sugar content, and available for actual production.
A kind of red wine alcoholic strength and total sugar content quantitative analysis method, include the following steps：
S100：The spectrum of the tested red wine of acquisition；
S200：Decayed using single-point ATR and be totally reflected test pattern；
S600：The alcoholic strength and total sugar content for obtaining the tested red wine quantify.
A kind of red wine alcoholic strength described further and total sugar content quantitative analysis method, it is right in 200 step
The tested red wine carries out alcoholic strength and total sugar content quantitative analytical instrument is infrared spectrometer or Fourier transform.
A kind of red wine alcoholic strength described further and total sugar content quantitative analysis method, after 200 step,
Further include following steps：S300：To being based on single-point ATR-FTIR (attenuation total reflection-FTIR spectrum) methods and stoichiometry
Learn (Partial Least Squares) be combined the prediction model of established its alcoholic strength of red wine quantitative analysis and total sugar content into
Row verification.
A kind of red wine alcoholic strength described further and total sugar content quantitative analysis method, the S300 steps include
Following steps：
S301：Using 9.0 analysis softwares of TQ Analyst (TQ Analyst are a general spectral analysis softwares, it
Can the application of infrared in, near-infrared, far infrared and Raman spectrum analysis various qualitative and quantitative analysis tools are provided.This is soft
Part is other than comprising various algorithmic tools, additionally it is possible to provide intuitive friendly, easy-to-use graphical interfaces and extensively to the user
Online help information.Use TQ Analyst cause method design and establish more sequencing, it is more purposive rather than
Dependent on conjecture.) PLS (Partial Least Squares) quantitative model is established (reference can be made to attached drawing 8,9 is respectively to be tied based on ATR-FTIR
Close PLS Partial Least Squares and build red wine alcohol and total sugar content quantitative model), before establishing prediction model, wave need to be selected
Long region, number of principal components and Pretreated spectra.
A kind of red wine alcoholic strength described further and total sugar content quantitative analysis method are wrapped after the S300 steps
Include following steps：
S401：Red wine at least one sample of known alcohol degree and total sugar content is chosen as external certificate sample；
S402：Peace is measured according to the S200 steps, and infrared spectrum acquisition parameter carries out spectral scan, and each sample is put down
Row scanning 6 times；
S403：At least one sample spectra is imported into the pre- of the alcoholic strength built up in above-mentioned S300 steps and total sugar content
It surveys in model, obtains the infrared predicted value of alcoholic strength and total sugar content；
S404：By the alcoholic strength measured value of the infrared predicted value and alcohol meter method carry out independent samples t test (T is examined,
Also known as student t examine (Student's t test), are mainly used for smaller (such as the n of sample content<30), population standard deviation
Normal distribution unknown σ.T inspections are the probability occurred with t distribution theorys come inference difference, so as to compare the difference of two average
It is different whether notable.)：Open SPSS17.0 softwares (SPSS (Statistical Product and Service
Solutions), full name is SPSS Statistics, is common software in statistics, for statistical analysis operation, data
Excavation, forecast analysis and decision support task dispatching.Provide data acquisition, data management and preparation, data analysis, result report
The complete procedure of such a data analysis, therefore the whole flow process of data analysis is comprehensively covered very much, it is particularly suitable for setting
Count the correlation graph in survey plan, and making and research for statistical analysis to data report.In addition, SPSS has completely
Data input, editor, statistical analysis, report, the functions such as graphic making.), by sample to be tested predicted value and actual value input pair
It answers in field, " analysis " → " comparing mean value " → independent sample T examines (T) → is selected to obtain a result in page pop-up, into
And judge whether that there were significant differences；
S405：The total sugar content measured value of the infrared predicted value and direct titrimetric method is carried out to match the t inspections；
S406：When the t values that sample to be tested obtains are less than t10 0.05(when carrying out t inspections, it is in inspection level to look into t distribution tables:α
=0.05, confidence level 95%, when degree of freedom f is 10, the numerical value that is checked in.) when, the t inspections set confidence level as 95%
When, it is proved to be successful.
A kind of red wine alcoholic strength described further and total sugar content quantitative analysis method, the S200 steps include
Following steps：
S201：4000~400cm-1 of scanning range, scanning signal add up 16 times, and resolution ratio is ± 4cm-1；
S202：Using savitzky-golay polynomial smoothings, (smooth effect is to improve signal-to-noise ratio, and reduction is made an uproar at random
Sound, so as to which the robustness of model can also be improved.TQ Analyst 9.0 (Thermo Fisher Scientific Inc.) are soft
Smoothing method is available there are two types of in part, and one of which is classical Savitzky-Golay filtering, it is a kind of multinomial
Filtering method.) second dervative spectrogram is obtained, setting points are 9.
A kind of red wine alcoholic strength described further and total sugar content quantitative analysis method, the S100 steps include
Following steps：
S101：The alcoholic strength content of the tested red wine is between 7.7%vol~15.2%vol；
S102：The total sugar content of the tested red wine is between 1.75g/L~66.96g/L.
A kind of red wine alcoholic strength described further and total sugar content quantitative analysis method are wrapped after the S300 steps
Include following steps：
S501：Generation is based on the ATR-FTIR technologies to the PLS quantitative models of red wine alcoholic strength；
S502：Generation is based on the ATR-FTIR technologies to the PLS quantitative models of red wine total sugar content.
A kind of red wine alcoholic strength described further and total sugar content quantitative analysis method, the tested red wine
For solid, liquid or gas.
The alcoholic strength and total sugar content of the domestic red wine of this fast quantification prediction proposed according to above technical scheme
Method, has the following advantages compared with prior art：
1st, this method is acquired wine sample using total reflection-FT-mid-IR fiber optics spectroscopy of decaying, and combines chemistry
Meterological processing method PLS carries out the alcoholic strength and total sugar content of the red wine of different wine types by establishing quantitative model
Forecast analysis.
2nd, this method need to only acquire the infrared spectrum of wine samples, without carrying out any physical treatment or chemistry to sample
It destroys, and does not consume other chemical reagent in the process, easy to be quick easy to operate, entire gatherer process carries significantly within 3min
High detection efficiency, and do not form destruction to environment.
Description of the drawings
The present invention is described in further detail with reference to the accompanying drawings and detailed description：
Fig. 1 is main flow schematic diagram of the present invention；
Fig. 2 is the accuracy test of 3 red wine alcoholic strength quantitative model of table of the present invention；
Fig. 3 is the accuracy test of 4 red wine total sugar content quantitative model of table of the present invention；
Fig. 4 be 1500~850cm-1 of the present invention and 3000~2800cm-1 wave bands it is lower four kinds typical case grape wine it is original red
External spectrum figure (GX1, BG1, BT1, TX1)；
Fig. 5 be lower four kinds typical grape wine of 1500~850cm-1 wave bands second dervative infrared spectrogram (GX1, BG1,
BT1,TX1)；
Fig. 6 be lower four kinds typical grape wine of 1200~950cm-1 wave bands second dervative infrared spectrogram (GX1, BG1,
BT1,TX1)；
Fig. 7 is the PLS quantitative models to red wine alcoholic strength based on ATR-FTIR technologies；
Fig. 8 is the PLS quantitative models to red wine total sugar content based on ATR-FTIR technologies.
Specific embodiment
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, explanation and attached drawing are for the present invention below
It is exemplary, and is understood not to the limitation present invention.Following description describe numerous details to facilitate to this hair
Sensible solution.However, in some instances, well known or conventional details does not specify simultaneously, to meet the succinct requirement of specification.
In a typical configuration of this application, it is calculated for model and the operation terminal of graph curve generation includes one
Or multiple processors (CPU), input/output interface, network interface and memory.
The operation terminal of being calculated for model in the present invention and graph curve generation includes processor, containing single core processor
Or multi-core processor.Processor is alternatively referred to as one or more microprocessors, central processing unit (CPU) etc..More specifically,
Processor can be that instruction set calculating (CISC) microprocessor, reduced instruction set computing (RISC) microprocessor, overlength of complexity refer to
Word (VLIW) microprocessor is enabled, realize the processor of other instruction set or realizes the processor of instruction set combination.Processor may be used also
For one or more application specific processors, such as application-specific integrated circuit (ASIC), field programmable gate array (FPGA), digital signal
Processor (DSP), network processing unit, graphics processor, network processing unit, communication processor, cipher processor, coprocessor,
Embeded processor or be capable of process instruction any other type logical block.Processor is begged for for performing the present invention
The operation of opinion and the instruction of step.
In the present invention for model calculate and graph curve generation operation terminal include memory, it may include one or
Multiple volatile storage devices, such as random access memory (RAM), dynamic ram (DRAM), synchronous dram (SDRAM), static state
RAM (SRAM) or other kinds of storage device.Memory can be stored including the finger by processor or the execution of any other equipment
Enable the information of sequence.For example, several operation systems, device driver, firmware (for example, input and output fundamental system or BIOS)
And/or the executable code and/or data of application program can be loaded in memory and be performed by processor.
The operating system of the operation terminal of being calculated for model in the present invention and graph curve generation can be any types
Operating system, such as Windows, Windows Phone of Microsoft, Apple Inc. IOS, the Android of Google,
And Linux, Unix operating system or other real-time or embedded OS VxWorks etc..
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, explanation and attached drawing are for the present invention below
It is exemplary, and is understood not to the limitation present invention.Following description describe numerous details to facilitate to this hair
Sensible solution.However, in some instances, well known or conventional details does not specify simultaneously, to meet the succinct requirement of specification.This
The specific of invention judges system and method referring to following embodiments：
First embodiment
A kind of method of the quick alcoholic strength and total sugar content for measuring red wine simultaneously, specifically includes following six operation
Step：
(1) red wine sample is collected；
(2) alcoholic strength and total sugar content of national standard method determination sample are utilized；
(3) ir data of sample is acquired；
(4) it is the ir data of each sample is related to alcoholic strength and total sugar content the value one-to-one correspondence measured
Connection, is fitted using chemo metric software, establishes quantitative model；
(5) verification of quantitative model；
(6) measure of the alcoholic strength of unknown red wine sample and total reducing sugar
The domestic different alcoholic strengths of different manufacturers and the red wine of total sugar content are collected by step (1).
The alcoholic strength of wine sample, GB/T 15038-2006 are measured using GB/T 15038-2006 alcohol meters method by step (2)
Direct titrimetric method measures total sugar content.
When carrying out the acquisition of infrared spectrum by step (3), Britain platinum Ai Ermo Spotlight 400 are utilized
(PerkinElmer Spotlight 400) Fourier transformation infrared spectrometer (subsidiary PerkinElmer Universal ATR
Sampling attachment) acquire respectively different wine types red wine infrared spectrum, dry type red wine is denoted as GX1, GX2 ..., half
Dry type is denoted as BG1, BG2 ..., and semi-sweet is denoted as BT1, BT2 ..., and sweet tea type is denoted as TX1, TX2 ...；
Decayed using single-point ATR and be totally reflected test pattern, scanning range 4000-400cm-1, scanning signal adds up 16 times, point
Resolution is ± 4cm-1, and obtain second dervative spectrogram, corresponding diagram 4, Fig. 5 and Fig. 6 using 9 multinomial least square methods are smooth.
PLS (Partial Least Squares) quantitative model is established using 9.0 analysis softwares of TQ Analyst according to step (4), is built
Before vertical calibration model, wavelength, number of principal components and Pretreated spectra need to be selected.
According to 4, the red wine sample of selection known alcohol degree and total sugar content in step (5), (content need to be in straightening die
Within type content range) as external certificate sample.Spectral scan is carried out by the infrared spectrum acquisition parameter in step (3), often
A sample parallel sweep 6 times.4 sample spectras are imported in the calibration model of alcoholic strengths and total sugar content, obtain alcoholic strength and
The predicted value of total sugar content.The measured value of infrared predicted value and alcohol meter method or direct titrimetric method is subjected to paired t-test, when setting
When fixation reliability is 95%, measured value that the predicted value that is obtained using the method for the present invention is obtained with alcohol meter method or direct titrimetric method
Between difference it is not notable.
This explanation using ATR-FTIR of the present invention (attenuation total reflection-FTIR spectrum), (be all-trans method by attenuation
Penetrate-FTIR spectrum technology (attenuated total reflectance-Fourier transform infrared
Spectroscopy, ATR-FTIR) spectral fingerprint feature in sample can be quickly detected, reflect that the molecular vibration in entire cell is special
Sign) measure red wine alcoholic strength and total sugar content be feasible.
According to the red wine sample that alcoholic strength and total sugar content to be measured are taken in step (6), according to the single-point in step (3)
ATR-FTIR methods acquisition parameter carries out IR spectrum scanning.Spectrum is directed respectively into alcoholic strength and total sugar content quantitative model,
The analysis result of alcoholic strength and total sugar content can quickly be obtained.
It should be noted that the present invention be suitable for red wine alcoholic strength content 7.7%vol~
Between 15.2%vol, total sugar content is between 1.75g/L~66.96g/L.With common domestic red Portugal on the market
The alcoholic strength and total sugar content range of grape wine are consistent.
Gained modeling result is that the related coefficient of alcoholic strength calibration set is 0.9586, calibration set root-mean-square error
(RMSEC) value is 0.387, and the related coefficient for verifying collection is 0.9648, and forecast set root-mean-square error (RMSEP) value is
0.353；The related coefficient of total reducing sugar calibration set is 0.9990, and calibration set root-mean-square error (RMSEC) value is 0.946, verifies collection
Related coefficient is 0.9991, and forecast set root-mean-square error (RMSEP) value is 0.946.T, which is examined, is also known as student t inspections
(Student's t test)：For testing model applicability, respectively using the red wine of different alcoholic strengths and total sugar content as sample
This (being labeled as sample A, B, C, D) is tested, each sample measures six times.
Acquired results look into t distribution tables：During f=n1+n2-2=10, if α=0.05, t10 0.05=1.812.tA、tB、tC、
TD values are respectively less than t10 0.05, i.e., in infrared analysis A, B, C, D samples between the predicted value and actual value of alcoholic strength and total sugar content not
There are significant differences, and when carrying out t inspections, it is in inspection level to look into t distribution tables:α=0.05, confidence level 95%, degree of freedom f
When being 10, the numerical value that is checked in.Show the red wine alcoholic strength built based on PLS methods and total sugar content respectively in 7.7-
The Quantitative Prediction Model of 15.2%vol, 1.75-66.96g/L work well, accurately can quickly measure red wine alcoholic strength and
Total sugar content, and available for actual production.
Table 1 is the parameter based on PLS method red wine alcoholic strength quantitative models
Table 2 is the parameter based on PLS method red wine total sugar content quantitative models
Table 3 and table 4, referring to Fig. 2 and Fig. 3.
Second implements
A kind of alcoholic strength and total reducing sugar for quickly measuring red wine simultaneously based on single-point ATR-FTIR of the present invention presented below
The specific embodiment of the method for content.
1. the collection of modeling sample：
The different alcoholic strengths of domestic different manufacturers different brands and the red wine sample of total sugar content are collected, altogether 336
Part red wine sample.
2. the measure of modeling sample parameter standard value：
The alcoholic strength of wine sample, GB/T 15038-2006 direct titrimetric methods are measured using GB/T 15038-2006 alcohol meters method
Measure total sugar content.
3. modeling sample ir data acquires：
Utilize Britain platinum Ai Ermo Spotlight 400 (PerkinElmer Spotlight 400) Fourier transform
Infrared spectrometer (subsidiary PerkinElmer Universal ATR samplings attachment) acquires the red wine of different wine types respectively
Infrared spectrum, dry type red wine are denoted as GX1, GX2 ..., and half-dry type is denoted as BG1, BG2 ..., and semi-sweet is denoted as BT1,
BT2 ..., sweet tea type are denoted as TX1, TX2 ...
Decayed using single-point ATR and be totally reflected test pattern, 4000~400cm of scanning range-1, scanning signal adds up 16 times,
Resolution ratio is ± 4cm-1, and obtain second dervative spectrogram, corresponding diagram 4, Fig. 5 and Fig. 6 using 9 multinomial least square methods are smooth.
4. the foundation of quantitative model：
(1) foundation of alcoholic strength quantitative model：Import alcoholic strength standard value after measured and known alcohol degree content
The original infrared spectrum of red wine sample to be measured, wherein the data of 224 samples establish calibration set, 112 sample datas are built
Vertical verification collection, ratio is close to 2:1, in 9.0 analysis softwares of TQ Analyst, first derivative pretreatment is carried out, and select to spectrum
It selects Savitzky-Golay Filtering (multinomial least square method) and 9 smoothing processings is carried out to spectrum, using TQ
9.0 analysis softwares of Analyst establish PLS quantitative models, and alcoholic strength wave band chooses 1500-850cm-1Range, this paragraph corresponding diagram
7。
(2) foundation of total reducing sugar quantitative model：Import total sugar content standard value after measured and known alcohol degree content
The original infrared spectrum of red wine sample to be measured, wherein the data of 224 samples establish calibration set, 112 sample datas are built
Vertical verification collection, ratio is close to 2:1, in 9.0 analysis softwares of TQ Analyst, first derivative pretreatment is carried out, and adopt to spectrum
9 smoothing processings are carried out to spectrum with Savitzky-Golay Filtering (multinomial least square method), using TQ
9.0 analysis softwares of Analyst establish PLS quantitative models, and total reducing sugar wave band chooses 1200~950cm-1And 3000~2800cm-1Model
It encloses, this paragraph corresponding diagram 8.
5. the verification of quantitative model：(content need to be in institute for 4, the red wine sample of selection known alcohol degree and total sugar content
Within established model content range) as external certificate sample.Spectrum is carried out by the infrared spectrum acquisition parameter in step (3) to sweep
It retouches, each sample parallel sweep 6 times.4 sample spectras are imported in the quantitative model of alcoholic strength and total sugar content, obtain alcohol
The predicted value of degree and total sugar content.The measured value of infrared predicted value and alcohol meter method or direct titrimetric method is subjected to paired t-test,
When set confidence level as 95% when, survey that the predicted value that is obtained using the method for the present invention is obtained with alcohol meter method or direct titrimetric method
Difference between definite value is not notable.(attenuation total reflection-Fourier is infrared using single-point ATR-FTIR of the present invention for this explanation
Spectrum) method measure red wine alcoholic strength and total sugar content be feasible.
6. the red wine sample of alcoholic strength and total sugar content to be measured is chosen, according to the single-point ATR-FTIR in step (3)
Method acquisition parameter carries out IR spectrum scanning.Spectrum is directed respectively into alcoholic strength and total sugar content calibration model, it can be quick
Obtain the analysis result of alcoholic strength and total sugar content.
It is obvious to a person skilled in the art that the present invention is not limited to the details of above-mentioned exemplary embodiment, Er Qie
In the case of without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended power
Profit requirement rather than above description limit, it is intended that all by what is fallen within the meaning and scope of the equivalent requirements of the claims
Variation includes within the present invention.Any reference numeral in claim should not be considered as to the involved claim of limitation.This
Outside, it is clear that one word of " comprising " is not excluded for other units or step, and odd number is not excluded for plural number.That is stated in device claim is multiple
Unit or device can also be realized by a unit or device by software or hardware.The first, the second grade words are used for table
Show title, and do not represent any particular order.
Claims (9)
1. a kind of red wine alcoholic strength and total sugar content quantitative analysis method, which is characterized in that include the following steps：
S100：The spectrum of the tested red wine of acquisition；
S200：Decayed using single-point ATR and be totally reflected test pattern；
S600：The alcoholic strength and total sugar content for obtaining the tested red wine quantify.
2. a kind of red wine alcoholic strength as described in claim 1 and total sugar content quantitative analysis method, which is characterized in that institute
It states in 200 steps, it is red for Fourier transformation to carry out alcoholic strength and total sugar content quantitative analytical instrument to the tested red wine
External spectrum instrument.
3. a kind of red wine alcoholic strength as described in claim 1 and total sugar content quantitative analysis method, which is characterized in that
After 200 step, following steps are further included：
S300：To being combined established its alcohol of red wine quantitative analysis with Chemical Measurement based on single-point ATR-FTIR methods
The prediction model of degree and total sugar content is verified.
4. a kind of red wine alcoholic strength as claimed in claim 3 and total sugar content quantitative analysis method, which is characterized in that institute
S300 steps are stated to include the following steps：
S301：PLS quantitative models are established using 9.0 analysis softwares of TQ Analyst, before establishing prediction model, wavelength need to be selected
Region, number of principal components and Pretreated spectra.
5. a kind of red wine alcoholic strength as claimed in claim 4 and total sugar content quantitative analysis method, which is characterized in that institute
Include the following steps after stating S300 steps：
S401：Red wine at least one sample of known alcohol degree and total sugar content is chosen as external certificate sample；
S402：Peace is measured according to the S200 steps, and infrared spectrum acquisition parameter carries out spectral scan, and each sample is parallel to be swept
It retouches 6 times；
S403：At least one sample spectra is imported to the prediction mould of the alcoholic strength built up in above-mentioned S300 steps and total sugar content
In type, the infrared predicted value of alcoholic strength and total sugar content is obtained；
S404：The alcoholic strength measured value of the infrared predicted value and alcohol meter method is subjected to independent samples t test：It opens
By in sample to be tested predicted value and actual value input corresponding data column, " analysis " is selected in page pop-up for SPSS17.0 softwares
→ " comparing mean value " → independent sample T examines (T) → obtains a result, and then judges whether that there were significant differences；
S405：The total sugar content measured value of the infrared predicted value and direct titrimetric method is carried out to match the t inspections；
S406：When the t values that sample to be tested obtains are less than t10 0.05When, t inspection set confidence level as 95% when, be proved to be successful.
6. a kind of red wine alcoholic strength as described in claim 1 and total sugar content quantitative analysis method, which is characterized in that institute
S200 steps are stated to include the following steps：
S201：4000~400cm of scanning range-1, scanning signal adds up 16 times, and resolution ratio is ± 4cm-1；
S202：Second dervative spectrogram is obtained using savitzky-golay polynomial smoothings, setting points are 9.
7. a kind of red wine alcoholic strength as claimed in claim 6 and total sugar content quantitative analysis method, which is characterized in that institute
S100 steps are stated to include the following steps：
S101：The alcoholic strength content of the tested red wine is between 7.7%vol~15.2%vol；
S102：The total sugar content of the tested red wine is between 1.75g/L~66.96g/L.
8. a kind of red wine alcoholic strength as claimed in claim 7 and total sugar content quantitative analysis method, which is characterized in that institute
Following steps are further included after stating S300 steps：
S501：Generation is based on the ATR-FTIR technologies to the PLS quantitative models of red wine alcoholic strength；
S502：Generation is based on the ATR-FTIR technologies to the PLS quantitative models of red wine total sugar content.
9. a kind of red wine alcoholic strength as claimed in claim 8 and total sugar content quantitative analysis method, which is characterized in that institute
Tested red wine is stated as solid, liquid or gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810057312.4A CN108226086A (en) | 2018-01-22 | 2018-01-22 | A kind of red wine alcoholic strength and total sugar content quantitative analysis method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810057312.4A CN108226086A (en) | 2018-01-22 | 2018-01-22 | A kind of red wine alcoholic strength and total sugar content quantitative analysis method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108226086A true CN108226086A (en) | 2018-06-29 |
Family
ID=62668054
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810057312.4A Pending CN108226086A (en) | 2018-01-22 | 2018-01-22 | A kind of red wine alcoholic strength and total sugar content quantitative analysis method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108226086A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111027025A (en) * | 2019-12-11 | 2020-04-17 | 华北电力大学（保定） | Method for screening infrared spectrum characteristic wavelength to predict wine quality parameters |
| CN111189817A (en) * | 2020-01-09 | 2020-05-22 | 中国原子能科学研究院 | Laser-induced breakdown spectroscopy true and false signal resolution data analysis method |
| CN111426636A (en) * | 2020-04-09 | 2020-07-17 | 米诺杰科技(江苏)有限公司 | Instrument for quickly analyzing chemical component content of wine |
| CN112505128A (en) * | 2020-11-30 | 2021-03-16 | 北方民族大学 | Method and device for nondestructive testing of reducing sugar of wine |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1214768A (en) * | 1996-02-02 | 1999-04-21 | 量度测试设备股份有限公司 | Method and apparatus for multi-spectral analysis in nonvinvasive infrared spectroscopy |
| CN101216418A (en) * | 2008-01-21 | 2008-07-09 | 浙江大学 | Bottle-contained yellow wine quality index on-line detection method and device |
| CN102175638A (en) * | 2011-01-05 | 2011-09-07 | 浙江科技学院 | Device for rapidly and nondestructively detecting component content of yellow rice wine |
| CN105911017A (en) * | 2016-04-12 | 2016-08-31 | 中华人民共和国张家港出入境检验检疫局 | Detection method for simultaneously and rapidly determining five indexes in wine |
-
2018
- 2018-01-22 CN CN201810057312.4A patent/CN108226086A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1214768A (en) * | 1996-02-02 | 1999-04-21 | 量度测试设备股份有限公司 | Method and apparatus for multi-spectral analysis in nonvinvasive infrared spectroscopy |
| CN101216418A (en) * | 2008-01-21 | 2008-07-09 | 浙江大学 | Bottle-contained yellow wine quality index on-line detection method and device |
| CN102175638A (en) * | 2011-01-05 | 2011-09-07 | 浙江科技学院 | Device for rapidly and nondestructively detecting component content of yellow rice wine |
| CN105911017A (en) * | 2016-04-12 | 2016-08-31 | 中华人民共和国张家港出入境检验检疫局 | Detection method for simultaneously and rapidly determining five indexes in wine |
Non-Patent Citations (5)
| Title |
|---|
| 常瑞红等: "近红外光谱快速分析成品葡萄酒指标的研究", 《酿酒科技》 * |
| 杜一平等: "《现代仪器分析方法》", 31 October 2008 * |
| 樊双喜等: "近红外光谱技术定量分析葡萄酒的主要成分", 《中国酿造》 * |
| 肖璞等: "不同厂家葡萄酒的红外光谱无损快速分析", 《光谱学与光谱分析》 * |
| 贾柳君等: "近红外光谱技术定量分析葡萄酒的主要成分", 《食品科技》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111027025A (en) * | 2019-12-11 | 2020-04-17 | 华北电力大学（保定） | Method for screening infrared spectrum characteristic wavelength to predict wine quality parameters |
| CN111189817A (en) * | 2020-01-09 | 2020-05-22 | 中国原子能科学研究院 | Laser-induced breakdown spectroscopy true and false signal resolution data analysis method |
| CN111189817B (en) * | 2020-01-09 | 2021-09-03 | 中国原子能科学研究院 | Laser-induced breakdown spectroscopy true and false signal resolution data analysis method |
| CN111426636A (en) * | 2020-04-09 | 2020-07-17 | 米诺杰科技(江苏)有限公司 | Instrument for quickly analyzing chemical component content of wine |
| CN112505128A (en) * | 2020-11-30 | 2021-03-16 | 北方民族大学 | Method and device for nondestructive testing of reducing sugar of wine |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108226086A (en) | A kind of red wine alcoholic strength and total sugar content quantitative analysis method | |
| CN103134767B (en) | Method for liquor quality identification through infrared spectrum revision | |
| CN101308086B (en) | Fruit internal quality on-line checking apparatus based on near infrared spectra technology | |
| CN105486655B (en) | The soil organism rapid detection method of model is intelligently identified based on infrared spectroscopy | |
| CN104897607A (en) | Food modeling and rapid detecting integration method and system adopting portable NIRS (near infrared spectroscopy) | |
| CN101216419A (en) | Method for quickly detecting yellow wine quality index | |
| CN107703097B (en) | Method for constructing model for rapidly predicting crude oil property by using near-infrared spectrometer | |
| CN105806825A (en) | On-line gas Raman analysis method for natural gas components | |
| CN102636450A (en) | Method for detecting wolfberry polyose content in Chinese wolfberry in a nondestructive way based on near infrared spectrum technology | |
| CN106770058A (en) | The quick special purpose device and its application method of the soil nitrate-N based on infrared spectrum | |
| CN105784672A (en) | Drug detector standardization method based on dual-tree complex wavelet algorithm | |
| CN109211829A (en) | A method of moisture content in the near infrared spectroscopy measurement rice based on SiPLS | |
| CN104596979A (en) | Method for measuring cellulose of reconstituted tobacco by virtue of near infrared reflectance spectroscopy technique | |
| CN115993344A (en) | Quality monitoring and analyzing system and method for near infrared spectrum analyzer | |
| CN101701911A (en) | Method for detecting content of reducing sugar in fermentation materials | |
| CN104596975A (en) | Method for measuring lignin of reconstituted tobacco by paper-making process by virtue of near infrared reflectance spectroscopy technique | |
| CN101349638A (en) | Optical spectrum rapid nondestructive detection method of fruit and vegetable vitamin C content | |
| CN104833652A (en) | Method for rapidly analyzing content of cellulose nitrate in mixed material | |
| CN100443883C (en) | Method for detecting hydrgenated tail-oil paraffin composition using near-infrared spectrum | |
| CN106442396A (en) | Rapidly detecting method for bagasse saccharose content based on near infrared technology | |
| CN111595807B (en) | Quantitative detection method for caprolactam in bio-based food packaging film | |
| CN111289459B (en) | Method, device, equipment and storage medium for detecting concentration of mixed substance components | |
| He et al. | Fast measurement of sugar content of yogurt using Vis/NIR-spectroscopy | |
| CN205506679U (en) | Portable near infrared spectroscopy detecting system | |
| CN107300535A (en) | The method of near-infrared quick detection organic fertilizer active constituent content |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Xu Changhua Inventor after: Hu Pozhen Inventor after: Zhu Li Inventor after: Tao Ningping Inventor after: Wang Xichang Inventor after: Yan Yu Inventor after: Zhang Xiaopeng Inventor after: Gu Dongchen Inventor before: Xu Changhua Inventor before: Hu Pozhen Inventor before: Tao Ningping Inventor before: Wang Xichang Inventor before: Yan Yu Inventor before: Zhang Xiaopeng Inventor before: Gu Dongchen |
|
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180629 |