CN108593861A - A method of prediction fresh-water fishes shelf life - Google Patents

A method of prediction fresh-water fishes shelf life Download PDF

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Publication number
CN108593861A
CN108593861A CN201810306580.5A CN201810306580A CN108593861A CN 108593861 A CN108593861 A CN 108593861A CN 201810306580 A CN201810306580 A CN 201810306580A CN 108593861 A CN108593861 A CN 108593861A
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shelf life
fresh
methyl
water fishes
pol
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乔宇
熊光权
张金木
廖李
汪兰
丁安子
吴文锦
李新
石柳
王俊
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Farm Product Processing and Nuclear Agricultural Technology Institute of Hubei Academy of Agricultural Sciences
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Farm Product Processing and Nuclear Agricultural Technology Institute of Hubei Academy of Agricultural Sciences
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    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/02Food
    • G01N33/12Meat; Fish

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Abstract

The invention discloses a kind of methods of prediction fresh-water fishes shelf life.This method is that the 3 kinds of odor compound methyl disulfides that will be measured under different temperatures, the concentration of 3 methyl, 1 butanol and 1 amylene, 3 alcohol in the flesh of fish have carried out kinetic model fitting with the changing rule of storage time, fresh-water fishes shelf life forecasting model is established, shelf life forecasting model is then based on and shelf life is evaluated.The method of prediction fresh-water fishes shelf life provided by the invention, the odor compound generated in storage using fish body come to fresh-water fishes degree of spoilage and freshness be detected, and for fish body fat content number, different objects is selected to establish model, predict fresh-water fishes shelf life, analysis detection time is short, operates rapid and convenient, compared to traditional microorganism and chemical index prediction technique, specific aim is stronger.

Description

A method of prediction fresh-water fishes shelf life
Technical field
The present invention relates to a kind of prediction techniques of fish shelf life, and in particular to a kind of side of prediction fresh-water fishes shelf life Method belongs to aquatic products Techniques of preserving field.
Background technology
China is fresh water fish production and consumption big country.Freshwater fish meat is full of nutrition, is rich in protein, amino acid and fat Fat, easily occurs putrid and deteriorated, and fish body during corruption, destroyed by musculature, and protein is under the action of enzyme point Solution is amino acid, and the smell distributed also becomes stink from original fishlike smell, and flavor quality reduces, or even will produce noxious material Jeopardize the health of consumer.With the continuous improvement of living standards, people are also higher and higher to the freshness requirements of fishery -ies product, because This is very necessary to the detection of its freshness and shelf life in fish body producing and selling and transporting procedures.
Currently, the prediction technique about fish shelf life mainly has sensory evaluation, microbiological indicator and physical and chemical index, using compared with More evaluation indexes mainly has Volatile Base Nitrogen, total plate count, K values, TBARS value etc..The detection of these methods is single Sample is time-consuming longer, cumbersome, can not accomplish quickly to detect.
Smell is one of the important indicator for evaluating Estimation of The Fish Freshness.The flesh of fish is in decay process, due to microorganism and itself The degradations such as the effect of enzyme, protein and fat will produce nitrogenous, amine, ammonia, alcohols and sulfur-bearing class volatile materials, can be by these Odor compound is applied to the prediction of Estimation of The Fish Freshness and shelf life, in addition, the fat content of fish body is different, the smell of generation It closes object will be different, therefore, it is also particularly important that the odor compound for selecting directive property strong is used as evaluation index.
Invention content
The object of the present invention is to provide a kind of methods of prediction fresh-water fishes shelf life, pass through the smell for selecting directive property strong Object is closed as evaluation index, and establishes prediction model, to realize the reasonable prediction to fresh-water fishes shelf life.
The invention is realized in this way:
A method of prediction fresh-water fishes shelf life, be the 3 kinds of odor compound methyl disulfides that will be measured under different temperatures, The concentration of 3- methyl-1-butanols and 1-POL in the flesh of fish has carried out kinetic model with the changing rule of storage time Fitting, establishes fresh-water fishes shelf life forecasting model, shelf life is evaluated and verified based on shelf life forecasting model, specifically Steps are as follows:
(1) fresh fish is slaughtered into cleaning, back meat is taken to be cut into small pieces, every piece of 20g ± 5g;
(2) by fish it is packaged enter valve bag, and be divided into four groups and be stored under different temperatures respectively, distinguish by intervals The content of fish 3 kinds of volatile scent compounds methyl disulfides in the block, 3- methyl-1-butanols and 1-POL is measured by sampling, And carry out subjective appreciation;
(3) data obtained according to step (2), establish containing for methyl disulfide, 3- methyl-1-butanols and 1-POL Amount obtains the reaction rate constant k of each compound with the kinetic model of storage temperature fluctuation;
(4) Arrhenius equation analysis temperature T and speed response constant k is utilized, to reaction rate constant under different temperatures K, which carries out curve fitting, obtains the frequency factor k of methyl disulfide, 3- methyl-1-butanols and 1-POL0And reaction activity EA
(5) shelf life forecasting model based on methyl disulfide, 3- methyl-1-butanols and 1-POL content is established,
SL is shelf life, and unit d, T are absolute temperature, unit K, A0For the content of initial odor compound, unit Ng/g, A are the content for storing the odor compound after the t times, unit ng/g, k0Frequency factor, EAReaction activity;
(6) prediction of fresh-water fishes shelf life:Shelf life is predicted with the shelf life forecasting model established.
Further scheme is:
In step (1), cleaning is that fish is put into trash ice, is cleaned with ice water or physiological saline;The fritter flesh of fish is thickness 2cm Long strip type sample, every piece of block weight 20g ± 5g.
Further scheme is:
In step (4) fresh-water fishes reserve temperature take respectively 271K, 273K, 277K, 281K i.e. -2 DEG C, 0 DEG C, 4 DEG C, 8 DEG C.
0-4 DEG C of selection is refrigerated storage temperature, and -2 DEG C are micro- jellys storages, 8 DEG C be meat in storing etc. entirely logistics progress often There is chain cleavage, temperature is caused to rise sharply.This 4 temperature are selected to cover in common cryopreservation temperature and transporting procedures Raised temperature after temperature fluctuation.
Further scheme is:
According to subjective appreciation as shelf life terminal, established in conjunction with Arrhenius equations and first order reaction kinetics model Shelf life forecasting model based on 3 kinds of odor compound methyl disulfides, 3- methyl-1-butanols and 1-POL.
Further scheme is:
In step (3), with level-one chemical reaction kinetic model to methyl disulfide, 3- methyl-1s-under different reserve temperatures Butanol and 1-POL carry out regression analysis, and regression equation expression formula is:A=A0×ekt, wherein A, A0, t, k respectively represent Quality factor number, initial value, time, reaction rate constant.
Further scheme is:
In step (4), with Arrhenius equationsK in formula0:Frequency factor;EA:Activation energy (J/ mol);T:Temperature (K);R:Gas constant, 8.3144J/ (molK), analysis temperature T and speed response constant k, will Arrhenius equations turned is lnk=lnk0-(EA/ RT), 1nk maps 1/T to obtain a straight line, and reaction is found out by straight slope Activation energyA, frequency factor k is found out by intercept0, the frequency factor k of methyl disulfide, 3- methyl-1-butanols and 1-POL0 With reaction activity EARespectively 4.4 × 108、1.35×108、1.65×109And 48.09kJmol-1、45.29kJ·mol-1、 50.83kJ·mol-1
Further scheme is:
In step (5), according to methyl disulfide, 3- methyl-1-butanols and 1-POL under 4 reserve temperatures gained The k arrived0Value and EAValue, is obtained by regression equation and Arrhenius equations: Calculate shelf life forecasting modelThe k that will be calculated0With reaction activity EAIt substitutes into This model obtains the shelf life forecasting model of methyl disulfide, 3- methyl-1-butanols and 1-POL;
Further scheme is:
Using the Analyses Methods for Sensory Evaluation Results of back fish block as shelf life terminal under different reserve temperatures, with above-mentioned forecasting shelf life The predicted value of model verifies shelf life with measured value.
Further scheme is:
For the fresh-water fishes of fat content≤5%, the forecasting shelf life established using methyl disulfide and 3- methyl n-butyl alcohols Model carries out forecasting shelf life;For fat content>5% fresh-water fishes, the forecasting shelf life mould established using 1-POL Type carries out forecasting shelf life.
The fat content range of common fresh-water fishes is as follows:
Further scheme is:
The fresh-water fishes are perch, Channel-catfish fishes, mandarin fish, Culter fishes, grass carp, black carp, bighead, silver carp, carp, crucian or bream Fish.
The method of prediction fresh-water fishes shelf life provided by the invention, the smell chemical combination generated in storage using fish body Object come to fresh-water fishes degree of spoilage and freshness be detected, and for fish body fat content number, select different mesh Mark object establishes model, carries out the prediction and verification of fresh-water fishes shelf life, and analysis detection time is short, operates rapid and convenient, compares and passes The microorganism of system and chemical index prediction technique, specific aim are stronger.
Description of the drawings
Fig. 1 is methyl disulfide in the flesh of fish under different reserve temperatures with the variation of storage time;
Fig. 2 is 3- methyl-1-butanols in the flesh of fish under different reserve temperatures with the variation of storage time;
Fig. 3 is 1-POL in the flesh of fish under different reserve temperatures with the variation of storage time;
Fig. 4 is subjective appreciation in the flesh of fish under different reserve temperatures with the variation of storage time.
Specific implementation mode
With reference to specific embodiment, the present invention is described in further detail.
As the specific embodiment of the present invention, in carrying out the present invention, it is necessary first to be set using following underlying instrument It is standby, including:
Weighing balance (BS-210, German Sai Duolisi), (XHF-D, Bo Xinzhi biotechnology share have interior cut type refiner Limit company), constant-temperature heating magnetic stirring apparatus (DF-101s, Wuhan Cole's experimental instruments and equipment limited), SPME extraction equipments (57330U, Supelco companies of the U.S.), 50/30 μm of DVB/CAR/PDMS of extracting head (Supelco companies of the U.S.), gas phase color Spectrum-mass spectrometer (GC7890A-MS5975B, Agilent companies of the U.S.).
It is, of course, understood that above-mentioned instrument and equipment is not limitation of the present invention, those skilled in the art can be with Use other instrument and equipments with same function.
Below to each step of the embodiment of the present invention and corresponding detection, analysis, computational methods detailed description.
Using perch as raw material, the full fish fats content of perch is 5-6%, is ground in early period for the experiment of the specific embodiment of the invention Find that different fingerlings are almost the same in the odor compound variation tendency of storage period on the basis of studying carefully, therefore can be according to the present invention The research of embodiment obtains the model that can promote the use of other type fresh-water fishes forecasting shelf lifes.
A method of prediction fresh-water fishes shelf life, including:
Step 1: pretreatment
It is cleaned with physiological saline after new fresh freshwater fish is slaughtered, removes the peel, back meat is taken to be cut into the strip pattern of thickness 2cm Product, every piece of 20g;
Step 2: detection and evaluation
By fish block be randomly divided into four be assembled into sterilizing valve bag be stored in tetra- different temperatures of 271K, 273K, 277K, 281K Under, by the separately sampled measurement of intervals;The time interval of sampling is:Start to sample daily, it is every later from second day Sampling is primary every two days;
Wherein, odor compound method for measuring is as follows:
It weighs the 6g chopping flesh of fish to be put in 50mL screw socket sample bottles, 12mL deionized waters is added, it is heat-insulated with polytetrafluoroethylene (PTFE) It seals, water-bath in magnetic stirring apparatus is placed at 60 DEG C and balances 15min, with 50/30 extracting head headspace absorptions of DVB/CAR/PDMS Extracting head is inserted into GC sample introductions, parses 5min, to be measured, each sample is 3 times parallel by 40min;
Chromatographic condition
Post case DB-WAX (the μ m 0.25mm of 30m × 0.25) equilibration time 1min, using temperature programming pattern, initial temperature 40 DEG C, 5min is kept, 90 DEG C are risen to 3 DEG C/min, 5min is kept, then 180 DEG C are risen to 8 DEG C/min, keeps 5min;Carrier gas (He) flow velocity 1.0mL/min;250 DEG C of injector temperature, does not shunt;
Mass Spectrometry Conditions
Ionization mode is EI;Mass Spectrometry Conditions are electron energy 70eV, voltage 350V;230 DEG C of ion source temperature, level four bars temperature 150 DEG C of degree, 280 DEG C of transmission line temperature;
Quantitative approach
Methyl disulfide, 3- methyl-1-butanols and 1-POL standard items are dissolved in methanol by a certain percentage to be configured to After knowing the mixed standard solution of content, 6 concentration gradients are diluted to deionized water, are separately added into wherein;Identical SPME, Extractive analysis is carried out under chromatographic condition and Mass Spectrometry Conditions, thus method obtains standard curve, according to standard curve and practical measurement Data calculate the content of methyl disulfide, 3- methyl-1-butanols and 1-POL in fish block;
Subjective appreciation
Color and luster, smell, tissue morphology and the tissue elasticity of the subjective appreciation primary evaluation flesh of fish, evaluating member is by 8 experts Composition, specific evaluation criteria are as shown in table 1;Experiment uses method of weighting scores, each index weights to be set as:Color and luster 20%, smell 30%, tissue morphology 30%, tissue elasticity 20%.It is the characteristic score value, each characteristic that the average mark of each characteristic, which is multiplied by its weight, The sum of for subjective appreciation point;
Subjective appreciation is as shown in Fig. 4 with the result of variations of storage time in the flesh of fish under different reserve temperatures;
1 sense organ evaluating meter of table
Step 3: the foundation of shelf life model
The foundation of first order reaction kinetics model
According to methyl disulfide, 3- methyl-1-butanols and 1-POL with storage time changing rule (such as attached drawing 1, 2, shown in 3), kinetic model of this 3 kinds of compounds with storage temperature fluctuation is established, can be the product for predicting and controlling fresh-water fishes Matter provides reliable theoretical foundation;In food processing and storage process, most of quality comparisons related with food quality are all Follow 1 grade of pattern;With level-one chemical reaction kinetic model to methyl disulfide under different reserve temperatures, 3- methyl-1-butanols and 1-POL carries out regression analysis, and relevant parameter is shown in Table 2;Regression equation expression formula is:A=A0×ekt(1), wherein A0For The content of initial odor compound, unit ng/g, A are the content for storing the odor compound after the t times, unit ng/g, when t is Between, k is reaction rate;
2 first-order kinetics parameter of table
k0And EAThe determination of value
With Arrhenius equations(k in formula0:Frequency factor;EA:Activation energy (J/ mol);T:Temperature (K);R:Constant, 8.3144J/ (molK)) analysis temperature T and speed response constant k, by the side Arrhenius Journey is converted into lnk=lnk0-(EA/ RT), 1nk maps to 1/T and a straight line can be obtained, and reaction activity can be found out by straight slope EA, frequency factor k can be found out by intercept0;Be computed, methyl disulfide, 3- methyl-1-butanols and 1-POL frequency factor k0With reaction activity EARespectively 4.4 × 108、1.35×108、1.65×109And 48.087kJmol-1、45.286kJ· mol-1、50.828kJ·mol-1
Shelf life forecasting model formula
According to methyl disulfide, 3- methyl-1-butanols and 1-POL under 4 reserve temperatures obtained k0Value and EA Value, can be obtained by publicity (1) and (2):Calculate shelf life forecasting model
The k that will be calculated0With reaction activity EAThis model is substituted into, methyl disulfide, 3- methyl-1-butanols and 1- are obtained The shelf life forecasting model of amylene -3- alcohol:
Step 4: the verification and evaluation of fresh-water fishes shelf life forecasting model
Sensory evaluation is allocated as the terminal for acceptable minimum gross score as shelf life using 5.When fresh-water fishes block reaches sense When official refuses point (reaching sensory evaluation 5 minutes), obtained with the content of methyl disulfide, 3- methyl-1-butanols and 1-POL Predicted value be compared with actual value, shelf life model is verified (such as table 3).When being verified, different fat have been selected The fish of fat content is verified respectively.
The fish of fat content≤5% is grass carp (271K), and bream (273K), crucian (277K), bighead (281K), fat contains Amount>5% fish is perch (271K), Channel-catfish fishes (273K), silver carp (277K) and carp (281K).
3 shelf life model verification result of table
Above-mentioned verification result shows, can quickly, relatively reliable in real time using the shelf life forecasting model that this research is established Predict the shelf life of fresh-water fishes under -2 DEG C of -8 DEG C of holding conditions.For the fresh-water fishes of fat content≤5%, using methyl disulfide and 3- methyl n-butyl alcohols establish shelf life forecasting model error it is smaller (<3%), for fat content>5% fresh-water fishes use 1-POL establish shelf life forecasting model error it is smaller (<3%).
Although reference be made herein to invention has been described for explanatory embodiment of the invention, and above-described embodiment is only this hair Bright preferable embodiment, embodiment of the present invention are not limited by the above embodiments, it should be appreciated that people in the art Member can be designed that a lot of other modification and implementations, these modifications and implementations will be fallen in principle disclosed in the present application Within scope and spirit.

Claims (10)

1. a kind of method of prediction fresh-water fishes shelf life, it is characterised in that:By measured under different temperatures 3 kinds of odor compounds two Two sulphur of first, the concentration of 3- methyl-1-butanols and 1-POL in the flesh of fish carry out dynamics with the changing rule of storage time Models fitting, establishes fresh-water fishes shelf life forecasting model, and specific step is:
(1) fresh fish is slaughtered into cleaning, back meat is taken to be cut into small pieces;
(2) by fish it is packaged enter valve bag, and be divided into four groups and be stored under different temperatures respectively, it is separately sampled by intervals The content for measuring fish 3 kinds of volatile scent compounds methyl disulfides in the block, 3- methyl-1-butanols or 1-POL, goes forward side by side Row subjective appreciation;
(3) data obtained according to step (2), establish the content of methyl disulfide, 3- methyl-1-butanols and 1-POL with The kinetic model of storage temperature fluctuation obtains the reaction rate constant k of each compound;
(4) Arrhenius equation analysis temperature T and speed response constant k are utilized, to reaction rate constant k under different temperatures into Row curve matching obtains the frequency factor k of methyl disulfide, 3- methyl-1-butanols and 1-POL respectively0And reaction activity EA
(5) shelf life forecasting model based on methyl disulfide, 3- methyl-1-butanols or 1-POL content is established,
SL is shelf life, unit d, R:Gas constant, 8.3144J/ (molK), T are absolute temperature, unit K, A0It is first The content of beginning odor compound, unit ng/g, A are the content for storing the odor compound after the t times, unit ng/g;
(6) shelf life forecasting model based on above-mentioned foundation carries out the verification and evaluation of the prediction model of fresh-water fishes shelf life:
Shelf life is verified with measured value with the predicted value of above-mentioned shelf life forecasting model.
2. the method for predicting fresh-water fishes shelf life according to claim 1, it is characterised in that:
In step (1), cleaning is that fish is put into trash ice, is cleaned with ice water or physiological saline;The fritter flesh of fish is the length of thickness 2cm Stripe shape sample, every piece of block weight 20g ± 5g.
3. the method for predicting fresh-water fishes shelf life according to claim 1, it is characterised in that:
Fresh-water fishes reserve temperature takes 271K, 273K, 277K, 281K respectively in step (2).
4. the method for predicting fresh-water fishes shelf life according to claim 1, it is characterised in that:
In step (3), shelf life terminal is determined according to the results of sensory evaluation of step (2), establishes methyl disulfide, 3- methyl-1s- The content of butanol and 1-POL with storage temperature fluctuation first order reaction kinetics model, and combine Arrhenius equations With methyl disulfide of the first order reaction kinetics model foundation based on 3 kinds of smells, the goods of 3- methyl-1-butanols and 1-POL Frame phase prediction model.
5. the method for predicting fresh-water fishes shelf life according to claim 4, it is characterised in that:
In step (3), with level-one chemical reaction kinetic model to methyl disulfide, 3- methyl-1-butanols under different reserve temperatures Regression analysis is carried out with 1-POL, regression equation expression formula is:A=A0×ekt, wherein A, A0, t, k respectively represent quality Because of subnumber, initial value, time, reaction rate constant.
6. the method for predicting fresh-water fishes shelf life according to claim 5, it is characterised in that:
In step (4), with Arrhenius equationsK in formula0:Frequency factor;EA:Activation energy, unit are J/mol;T:Temperature, unit K;R:Gas constant, 8.3144J/ (molK), analysis temperature T and speed response constant k, will Arrhenius equations turned is lnk=lnk0-(EA/ RT), 1nk maps 1/T to obtain a straight line, and reaction is found out by straight slope Activation energyA, frequency factor k is found out by intercept0, the frequency factor k of methyl disulfide, 3- methyl-1-butanols and 1-POL0 With reaction activity EARespectively 4.4 × 108、1.35×108、1.65×109And 48.087kJmol-1、45.286kJ· mol-1、50.828kJ·mol-1
7. the method for predicting fresh-water fishes shelf life according to claim 6, it is characterised in that:
In step (5), according to methyl disulfide, 3- methyl-1-butanols and 1-POL under 4 reserve temperatures obtained k0 Value and EAValue, is obtained by regression equation and Arrhenius equationsCalculate shelf Phase prediction modelThe k that will be calculated0With reaction activity EAThis model is substituted into, is obtained Shelf life forecasting model based on methyl disulfide, 3- methyl-1-butanols and 1-POL;
8. the method for predicting fresh-water fishes shelf life according to claim 1, it is characterised in that:
It is to use shelf using the Analyses Methods for Sensory Evaluation Results of back fish block as shelf life terminal under different reserve temperatures in step (6) The predicted value of phase prediction model verifies shelf life with measured value.
9. the method for predicting fresh-water fishes shelf life according to claim 1, it is characterised in that:
For the fresh-water fishes of fat content≤5%, the shelf life forecasting model established using methyl disulfide and 3- methyl n-butyl alcohols Carry out forecasting shelf life;For fat content>5% fresh-water fishes, using 1-POL establish shelf life forecasting model into Row forecasting shelf life.
10. according to the method for predicting fresh-water fishes shelf life described in claim 1 to 9 any claim, it is characterised in that:
The fresh-water fishes are perch, Channel-catfish fishes, mandarin fish, Culter fishes, grass carp, black carp, bighead, silver carp, carp, crucian or bream.
CN201810306580.5A 2018-04-08 2018-04-08 A method of prediction fresh-water fishes shelf life Pending CN108593861A (en)

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Application publication date: 20180928