CN102336996A - Time-temperature color-changing indicator and application and using method thereof - Google Patents

Time-temperature color-changing indicator and application and using method thereof Download PDF

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CN102336996A
CN102336996A CN201110167000.7A CN201110167000A CN102336996A CN 102336996 A CN102336996 A CN 102336996A CN 201110167000 A CN201110167000 A CN 201110167000A CN 102336996 A CN102336996 A CN 102336996A
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pda
vesica
concentration
blend
time
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CN102336996B (en
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钱志勇
魏于全
苟马玲
赵霞
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Sichuan University
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Sichuan University
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Abstract

The invention relates to a time-temperature color-changing indicator and application and a using method thereof, belonging to the technical fields of monitoring of vaccine and medicament storage. The time-temperature color-changing indicator comprises a polydiacetylene (PDA) vesicle and an amphiphilic polymer aqueous solution, wherein the PDA vesicle is formed by polymerizing a diacetylene substance shown as a formula I after self-assembly, and is shown as a formula II; and in the formula II, R refers to a hydrophilic group, and R' refers to a chain segment of a hydrophobic group. The time-temperature color-changing indicator is used for monitoring temperature change and time change within the temperature range of 0-50 DEG C, such as time and temperature changes and the like during monitoring of vaccine and bio-medicament transportation. The time-temperature color-changing indicator is convenient to use, is simple and effective, and is an indicator with practical application prospect.

Description

A kind of time-temperature decolored indicator and application and method of use
Technical field
The present invention relates to a kind of time-temperature decolored indicator, particularly based on gather diacetylene time-the temperature decolored indicator, belong to the technical field of transportations such as monitoring food, vaccine.
Background technology
The quality height of food and other perishable prod (like fresh foods prods, vaccine, some medicine etc.) depends on storage requirement and transport condition; As from producing or conditions such as temperature and the storage time of packing in during its last this section of the ultimate consumer of arrival; Elongated along with the rising of temperature and time; Because the increase of biochemical reaction speed makes the deterioration process accelerate; Therefore, need in these Product transport processes under the condition that is no more than the specified temp restriction, to store, perhaps period of storage can not exceed preset time at interval at least.
Current, general only guarantee the quality of storing, and only use date stamp with date stamp, can't the information of the storage requirement that has exposed therein about this product be provided to human consumer or other people in fact.For example, certain food is demarcated to storage temperature is 4 ℃, and shelf-lives is 7 days, if Food preservation is being higher than under 4 ℃ of conditions, will cause food just putrid and deteriorated before shelf-lives does not arrive; Otherwise if storage temperature is 0 ℃, the time of this based food storage just is longer than 7 days, if still by its predetermined shelf-lives, surpass 7 days and be dropped with regard to thinking it to go bad, will certainly cause the waste of high quality food.This shows, only be used for indicating use-by date, be difficult to guarantee Food Quality or cause waste.Therefore, as in the perishable prod distribution chain from the factory to human consumer, the monitoring of storing and transporting perishable prod time and temperature is then had great importance.
At present; General duration of service-TI is monitored the real shelf-life of each item product; Time temperature indicator (TTI) is defined as a kind of easy device; Can appear be easy to measure and with the variation of time and temperature correlation, this variation can reflect all or part of temperature history that adheres to product.
EP505449B1 discloses a part process time-TI; Comprising a kind of meltability material; For example polycaprolactone triol, Zusoplast 9002 C1-4 alkyl oxide and Z 150PH, when exceeding a given threshold temperature, they are in flow state; And when being exposed to the temperature that is lower than same temperature, they solidify again.The meltability material flows on a substrate, and when meltability material flow therein, an indicator system just produces a kind of ability with the detected variation of physical method on substrate.
Domestic relevant report about time-temperature indicator is less at present, and in the perishable prod distribution chain from the factory to human consumer, the monitoring of storing and transporting perishable prod time and temperature is then had great importance, and therefore needs more research.
Summary of the invention
The invention provides a kind of be suitable in 0～50 ℃ of TR time-temperature decolored indicator (TTI); The temperature variation and/or the time that are used for monitoring perishable object storing such as vaccine, biologics and transportation change, and TTI of the present invention is easy to use, effectively simple.
Technical scheme of the present invention:
The invention provides a kind of time-temperature indicator, it comprises PDA (the gathering diacetylene) vesica and the amphipathic nature polyalcohol aqueous solution, and wherein, the PDA vesica is to be formed by diacetylene class material (shown in the formula I) self-assembly post polymerization, and the PDA vesica is suc as formula shown in the II:
M is 5～500, and n is 5～500; Preferred m is 10～20, and n is 3～10;
In the formula, R is a hydrophilic radical, and said hydrophilic radical contains-COOH ,-NH 2Or-OH; R ' is a hydrophobic grouping, and said hydrophobic grouping contains:
-CH 2，
Figure BDA0000069854780000022
x＝1～10，
Figure BDA0000069854780000023
Wherein, the above-mentioned amphipathic nature polyalcohol aqueous solution is selected from Bai Luoshamu, Tween-20, Tween-80, OP-10, PCL-PEG or PVP.
Preferably, the concentration of the above-mentioned amphipathic nature polyalcohol aqueous solution is 0.001～50wt%.
Wherein, above-mentioned diacetylene class material is 10,12-tricosyl diacetylenic acid (PCDA), 2,4-heneicosyl diacetylenic acid (HCDA), 2,4-pentadecyl diacetylenic acid (PDDA) or 2,4-tricosyl diacetylenic acid (TCDA).
The present invention has also pointed out the application that temperature variation and/or the time of above-mentioned time-temperature decolored indicator in 0～50 ℃ of TR of monitoring changes.
Temperature and/or time that time-temperature indicator of the present invention can be used for monitoring in the perishable article transportation change, and the temperature and/or the time that are preferred for monitoring in vaccine, the biologics transportation change; Also can be used for the variation of monitoring of environmental temperature variation and/or time.
Preferably, being used for monitoring 50 ℃ of time-temperature indicators of preserving the article that are no more than 5min down is selected from: PDA vesica and concentration are that F127 blend, PDA vesica and the concentration of 2wt% is that F68 blend, PDA vesica and the concentration of 10wt% is that L35 blend, PDA vesica and the concentration of 5wt% is Tween-20 blend at least a of 0.5wt%; Or
Being used to monitor 50 ℃ of time-temperature indicators of preserving the article that are no more than 10min down is: PDA vesica and concentration are the F127 blend of 0.5wt%; Or
Being used to monitor 40 ℃ of time-temperature indicators of preserving the article that are no more than 1h down is: PDA vesica and concentration are the F127 blend of 0.5wt%; Or
Being used to monitor 40 ℃ of time-temperature indicators of preserving the article that are no more than 30min down is: PDA vesica and concentration are the F127 blend of 2wt%; Or
Being used for monitoring 40 ℃ of time-temperature indicators of preserving the article that are no more than 5min down is selected from: PDA vesica and concentration are that F127 blend, PDA vesica and the concentration of 10wt% is that F68 blend, PDA vesica and the concentration of 15wt% is that L35 blend, PDA vesica and the concentration of 10wt% is Tween-20 blend at least a of 5wt%; Or
Being used for monitoring 30 ℃ of time-temperature indicators of preserving the article that are no more than 4h down is: PDA vesica and concentration are that F127 blend, PDA vesica and the concentration of 5wt% is Tween-20 blend at least a of 5wt%; Or
Being used to monitor 30 ℃ of time-temperature indicators of preserving the article that are no more than 2h down is: PDA vesica and concentration are the Tween-20 blend of 15wt%; Or
Being used to monitor the time-temperature indicator of preserving the article that are no more than 1h under 86 ° of F is: PDA vesica and concentration are the Tween-20 blend of 10wt%; Or
Being used for monitoring 30 ℃ of time-temperature indicators of preserving the article that are no more than 30min down is selected from: PDA vesica and concentration are that F127 blend, PDA vesica and the concentration of 10wt% is Tween-20 blend at least a of 20wt%; Or
Being used for monitoring 30 ℃ of time-temperature indicators of preserving the article that are no more than 5min down is selected from: PDA vesica and concentration are that F68 blend, PDA vesica and the concentration of 30wt% is that L35 blend, PDA vesica and the concentration of 40wt% is Tween-20 blend at least a of 30wt%; Or
Being used to monitor 20 ℃ of time-temperature indicators of preserving the article that are no more than 48h down is: PDA vesica and concentration are the Tween-20 blend of 15wt%; Or
Being used to monitor 20 ℃ of time-temperature indicators of preserving the article that are no more than 24h down is: PDA vesica and concentration are the Tween-20 blend of 20wt%; Or
Being used to monitor 20 ℃ of time-temperature indicators of preserving the article that are no more than 4h down is: PDA vesica and concentration are the F127 blend of 15wt%; Or
Being used for monitoring 20 ℃ of time-temperature indicators of preserving the article that are no more than 2h down is selected from: PDA vesica and concentration are that F127 blend, PDA vesica and the concentration of 20wt% is Tween-20 blend at least a of 30wt%; Or
Being used for monitoring 20 ℃ of time-temperature indicators of preserving the article that are no more than 30min down is selected from: PDA vesica and concentration are that F68 blend, PDA vesica and the concentration of 40wt% is Tween-20 blend at least a of 40wt%; Or
Being used to monitor 20 ℃ of time-temperature indicators of preserving the article that are no more than 5min down is: PDA vesica and concentration are the Tween-20 blend of 50wt%; Or
Being used to monitor 10 ℃ of time-temperature indicators of preserving the article that are no more than 4h down is: PDA vesica and concentration are the Tween-20 blend of 40wt%; Or
Being used to monitor 10 ℃ of time-temperature indicators of preserving the article that are no more than 30min down is: PDA vesica and concentration are the Tween-20 blend of 50wt%.
Preferably, adopt the temperature variation in the time temperature indicator monitoring certain hour of the present invention, be specially:
A, b, c, four kinds of time-temperature indicators of d and article put together the temperature variation of article in the monitoring 5min, wherein:
The a telltale is selected from: PDA vesica and concentration are that F127 blend, PDA vesica and the concentration of 2wt% is that F68 blend, PDA vesica and the concentration of 10wt% is that L35 blend, PDA vesica and the concentration of 5wt% is at least a in the Tween-20 blend of 0.5wt%;
The b telltale is selected from: PDA vesica and concentration are that F127 blend, PDA vesica and the concentration of 10wt% is that F68 blend, PDA vesica and the concentration of 15wt% is that L35 blend, PDA vesica and the concentration of 10wt% is at least a in the Tween-20 blend of 5wt%;
The c telltale is selected from: PDA vesica and concentration are that F68 blend, PDA vesica and the concentration of 30wt% is that L35 blend, PDA vesica and the concentration of 40wt% is at least a in the Tween-20 blend of 30wt%;
The d telltale is that PDA vesica and concentration are the Tween-20 blend of 50wt%; Or
E, two kinds of time-temperature indicators of f and article put together the temperature variation of article in the monitoring 10min, wherein:
The e telltale is that PDA vesica and concentration are the F127 blend of 0.5wt%;
The f telltale is that PDA vesica and concentration are the Tween-20 blend of 10wt%; Or
G, h, i, four kinds of time-temperature indicators of j and article put together the temperature variation of article in the monitoring 30min, wherein:
The g telltale is that PDA vesica and concentration are the F127 blend of 2wt%;
The h telltale is selected from: PDA vesica and concentration are that F127 blend, PDA vesica and the concentration of 10wt% is at least a in the Tween-20 blend of 20wt%;
The i telltale is selected from: PDA vesica and concentration are that F68 blend, PDA vesica and the concentration of 40wt% is at least a in the Tween-20 blend of 40wt%;
The j telltale is that PDA vesica and concentration are the Tween-20 blend of 50wt%; Or
K, l, three kinds of time-temperature indicators of m and article put together the temperature variation of article in the monitoring 4h, wherein:
The k telltale is selected from: PDA vesica and concentration are that F127 blend, PDA vesica and the concentration of 5wt% is at least a in the Tween-20 blend of 5wt%;
The l telltale is: PDA vesica and concentration are the F127 blend of 15wt%;
The m telltale is: PDA vesica and concentration are the Tween-20 blend of 40wt%; Or
N, two kinds of time-temperature indicators of o and article put together the temperature variation of article in the monitoring 2h, wherein:
The n telltale is: PDA vesica and concentration are the Tween-20 blend of 15wt%;
The o telltale is selected from: PDA vesica and concentration are that F127 blend, PDA vesica and the concentration of 20wt% is at least a in the Tween-20 blend of 30wt%.
Preferably, the time in the time temperature indicator monitoring certain temperature range of the present invention of adopting changes, and is specially:
The time change histories of article in A, two kinds of time-temperature indicators of B and article put together and monitor 50 ℃, wherein:
The A telltale is selected from: PDA vesica and concentration are that F127 blend, PDA vesica and the concentration of 2wt% is that F68 blend, PDA vesica and the concentration of 10wt% is that L35 blend, PDA vesica and the concentration of 5wt% is at least a in the Tween-20 blend of 0.5wt%;
The B telltale is: PDA vesica and concentration are the F127 blend of 0.5wt%; Or
The time of article changed in C, D, three kinds of time-temperature indicators of E and article put together and monitor 40 ℃, wherein:
The C telltale is: PDA vesica and concentration are the F127 blend of 0.5wt%;
The D telltale is: PDA vesica and concentration are the F127 blend of 2wt%;
The E telltale is selected from: PDA vesica and concentration are that F127 blend, PDA vesica and the concentration of 10wt% is that F68 blend, PDA vesica and the concentration of 15wt% is that L35 blend, PDA vesica and the concentration of 10wt% is at least a in the Tween-20 blend of 5wt%; Or
The time of article changed in F, G, H, I, five kinds of time-temperature indicators of J and article put together and monitor 30 ℃, wherein:
The F telltale is selected from: PDA vesica and concentration are that F127 blend, PDA vesica and the concentration of 5wt% is at least a in the Tween-20 blend of 5wt%;
The G telltale is: PDA vesica and concentration are the Tween-20 blend of 15wt%;
The H telltale is: PDA vesica and concentration are the Tween-20 blend of 10wt%;
The I telltale is selected from: PDA vesica and concentration are that F127 blend, PDA vesica and the concentration of 10wt% is at least a in the Tween-20 blend of 20wt%;
The J telltale is selected from: PDA vesica and concentration are that F68 blend, PDA vesica and the concentration of 30wt% is that L35 blend, PDA vesica and the concentration of 40wt% is at least a in the Tween-20 blend of 30wt%; Or
The time of article changed in K, L, M, N, O, six kinds of time-temperature indicators of P and article put together and monitor 20 ℃, wherein:
The K telltale is: PDA vesica and concentration are the Tween-20 blend of 15wt%;
The L telltale is: PDA vesica and concentration are the Tween-20 blend of 20wt%;
The M telltale is: PDA vesica and concentration are the F127 blend of 15wt%;
The N telltale is selected from: PDA vesica and concentration are that F127 blend, PDA vesica and the concentration of 20wt% is at least a in the Tween-20 blend of 30wt%;
The O telltale is selected from: PDA vesica and concentration are that F68 blend, PDA vesica and the concentration of 40wt% is at least a in the Tween-20 blend of 40wt%;
The P telltale is: PDA vesica and concentration are the Tween-20 blend of 50wt%; Or
The time of article changed in Q, two kinds of time-temperature indicators of R and article put together and monitor 10 ℃, wherein:
The Q telltale is: PDA vesica and concentration are the Tween-20 blend of 40wt%;
The R telltale is: PDA vesica and concentration are the Tween-20 blend of 50wt%.
The present invention also provides the method for use of above-mentioned time-temperature decolored indicator, and concrete steps are:
(1) it is subsequent use to dispose the amphipathic nature polyalcohol aqueous solution and the PDA vesica of desired concn respectively;
(2) with the amphipathic nature polyalcohol aqueous solution that configures and the blend of PDA vesica, blend and article put together;
(3) mixture colour-change indicative for environments temperature variation in the above-mentioned steps 2 and/or time change; Or indicate monitored article to surpass suitable temperature and/or the time of preserving.
Beneficial effect of the present invention:
Adopt time-temperature indicator of the present invention, can be used for monitoring the time-temperature that vaccine, biologics, biotinylation kit etc. are easy to the material that temperature addles and change; The time and/or the temperature variation that also can be used for monitoring of environmental.TTI of the present invention is convenient and swift, need not to destroy original food product pack, is a kind of monitor with actual application prospect.
Description of drawings
Fig. 1: PDA vesica and amphipathic nature polyalcohol time-the preparation synoptic diagram of temperature decolored indicator.
Fig. 2: PDA/ different concns F127 places the colour-change figure of different time back pointer under the differing temps.
Fig. 3: the variable color degree (CR) of quantitatively determined PDA/F127 telltale.For quantitatively confirm color from indigo plant to red intensity of variation, available following formula quantitative Analysis CR:CR (%)=[(PB 0-PB 1)/PB 0] * 100; Specifically be that the 0.15mL sample is joined in 96 orifice plates, test absorbance value fast at 640nm and 550nm with spectrophotometer (M5, Molecular Corporation).
PB=A wherein Blue/ (A Blue+ A Red).
A is the absorption value in blue (640nm) or red (550nm) component;
PB 0Be the blue ratio of pure PDA liquid under 0 degree, as contrast;
PB 1It is the blue ratio after sample meets with differing temps and different time.
Fig. 4: PDA/F68 under the differing temps (a) and PDA/L35 (b) place the colour-change figure of different time back pointer.
Fig. 5: PDA/Tween-20 places the colour-change figure of different time back pointer under the differing temps.
The making of above-mentioned Fig. 2, Fig. 4, Fig. 5: selected concrete amphipathic nature polyalcohol; The amphipathic nature polyalcohol aqueous solution blend of configuration PDA/ different concns; In differing temps, different time point; Take the color of the amphipathic nature polyalcohol aqueous solution blend of PDA/ different concns, production standard look version with digital camera.
As shown in Figure 1, according to behind the colourless PCDA vesica of self-assembly, PDA forms through the ultraviolet width of cloth; Because hydrophobic interaction, the hydrophobic segment of amphipathic nature polyalcohol being inserted in the PDA vesica gradually adds the synergy of temperature; The conformational change that causes PDA jointly, thus colour-change takes place; This variation depends on the character of temperature, time and amphipathic nature polyalcohol.
As shown in Figure 2:
Under 0 ℃, 10 ℃, the PDA/F127 telltale along with the variation (0.1-20wt%) of F127 concentration respectively through 3 days with 24h all do not take place macroscopic from indigo plant to red colour-change;
In the time of 20 ℃, when F127 concentration is 20wt%, begin to change red, along with the prolongation color of time becomes dark red (becoming redness fully like the 24h color) by reddish brown by blueness through the 2h telltale; When F127 concentration is 15wt%, begin to change red through the 4h telltale by blueness, along with the prolongation color of time by reddish brown become dark red; When F127 concentration during less than 15wt%, through also not variable color of 24h;
In the time of 30 ℃, when F127 concentration is 10wt%, 15wt%, 20wt%, begin to change red, along with the prolongation color of time becomes dark red (becoming redness fully like color behind the 2h) by reddish brown by blueness through the 30min telltale; When F127 concentration is 5wt%, begin to change red through the 4h telltale, along with the prolongation color of time becomes dark red (becoming redness fully like color behind the 24h) by reddish brown by blueness; When F127 concentration during less than 5wt%, through also not variable color of 48h;
In the time of 40 ℃, when F127 concentration is 10,15, during 20wt%, begin to change red by blueness through the 5min telltale, along with the prolongation color of time becomes dark red (becoming redness fully like color behind the 30min) by reddish brown; When F127 concentration is 2wt%, begin to change red through the 30min telltale, along with the prolongation color of time becomes dark red (becoming redness fully like color behind the 1h) by reddish brown by blueness; When F127 concentration is 0.5wt%, begin to change red through the 1h telltale, along with the prolongation color of time becomes dark red (becoming redness fully like color behind the 8h) by reddish brown by blueness; When F127 concentration during less than 0.5wt%, through also not variable color of 48h;
In the time of 50 ℃, when F127 concentration is 20,15,10,5, during 2wt%, begin to change red by blueness through the 5min telltale, along with the prolongation color of time becomes dark red (becoming redness fully like color behind the 10min) by reddish brown; When F127 concentration is 1, during 0.5wt%, begin to change red by blueness through the 10min telltale, along with the prolongation color of time becomes dark red (becoming redness fully like color behind the 15min) by reddish brown; When F127 concentration is 0.2, during 0.1wt%, begin to change red by blueness through the 15min telltale, along with the prolongation color of time becomes dark red (becoming redness fully like color behind the 24h) by reddish brown; When F127 concentration during less than 0.1wt%, through also not variable color of 48h.We can see that the concentration of F127 is high more, and the color transition temperature is low more, and color transition speed is fast more; Simultaneously, temperature is high more, and color transition is fast more.
As shown in Figure 3: quantitative analysis the color transition of PDA/F127, when the concentration of F127 remains on 20%, CR is along with the increase of the growth of time and temperature and increase that (Fig. 3 is a); Remained 2 hours when the reaction times, CR increases (Fig. 3 b) along with the concentration increase of temperature and F127; When temperature remains on 30 ℃, CR increases with the concentration of F127 in time and increases (Fig. 3 c).Above results suggest PDA/F127 possibly become significant time of a kind of potential-temperature decolored indicator.
Shown in Fig. 4 (a):
Under 0 ℃, 10 ℃, the PDA/F68 telltale along with the variation (0.1-40wt%) of F68 concentration through do not take place in 3 days yet macroscopic from indigo plant to red colour-change;
In the time of 20 ℃, when F68 concentration is 40wt%, begin to change red, along with the prolongation color of time becomes dark red (when lasting 48h still for reddish brown) by reddish brown by blueness through the 30min telltale; When F68 concentration during less than 40wt%, through also not variable color of 48h;
In the time of 30 ℃, when F68 concentration is 40, during 30wt%, begin to change red by blueness through the 5min telltale, along with the prolongation color of time becomes dark red (becoming redness fully like color behind the 2h) by reddish brown; When F68 concentration during less than 30wt%, through also not variable color of 48h;
In the time of 40 ℃, when F68 concentration is 40,30,25,20, during 15wt%, begin to change red by blueness through the 5min telltale, along with the prolongation color of time becomes dark red (becoming redness fully greater than color behind 15% o'clock 5min like concentration) by reddish brown; When F68 concentration during less than 15wt%, through also not variable color of 48h;
In the time of 50 ℃, when F68 concentration is 40,30,25,20,15, during 10wt%, begin to change red by blueness through the 5min telltale, along with the prolongation color of time becomes dark red (becoming redness fully greater than color behind 10% o'clock 5min like concentration) by reddish brown; When F68 concentration during less than 10wt%, through also not variable color of 48h.
Shown in Fig. 4 (b):
Under 0 ℃, 10,20 ℃, the PDA/L35 telltale along with the variation (0.1-40wt%) of L35 concentration respectively through 3 days, 3 days, 48h do not take place yet macroscopic from indigo plant to red colour-change;
In the time of 30 ℃, when L35 concentration is 40wt%, begin to change red, along with the prolongation color of time becomes dark red (still being red-brown through 48h) by reddish brown by blueness through the 5min telltale; When L35 concentration during less than 40wt%, through also not variable color of 48h;
In the time of 40 ℃, when F68 concentration is 40,30,25,20,15, during 10wt%, begin to change red by blueness through the 5min telltale, along with the prolongation color of time becomes dark red (becoming redness fully greater than color behind 25% o'clock 5min like concentration) by reddish brown; When L35 concentration during less than 10wt%, through also not variable color of 48h;
In the time of 50 ℃, when F68 concentration is 40,30,25,20,15,10, during 5wt%, begin to change red by blueness through the 5min telltale, along with the prolongation color of time becomes dark red (becoming redness fully greater than color behind 5% o'clock 5min like concentration) by reddish brown; When L35 concentration during less than 5wt%, through also not variable color of 48h;
We can see by Fig. 4, and F68 and L35 show that to the color influence of PDA vesica the colour-change of visible temperature, polymer concentration dependence can both take place for PDA/F68 and PDA/L35, and polymer concentration is high more, and the color transition temperature is low more; From PDA/F127 to PDA/F68 to PDA/L35; The time-dependent manner of color transition progressively weakens, and this possibly be inserted among the PDA relevant with molecular weight because of PEG-PPG-PEG, and molecular weight is big more; The speed that is inserted among the PDA is slow more, thereby the colour-change of PDA is also slow more.
As shown in Figure 5:
Under 0 ℃, when Tween-20 concentration was 50wt%, the PDA/Tween-20 telltale began to change red through the 48h color by blueness;
In the time of 10 ℃, when Tween-20 concentration was 40wt%, telltale began to change red through the 4h color by blueness; When Tween-20 concentration was 50wt%, telltale began to change red (still being reddish brown during 48h) through the 30min color by blueness; When Tween-20 concentration during less than 40wt%, through also not variable color of 48h;
In the time of 20 ℃, when Tween-20 concentration was 50wt%, telltale began to change red (becoming dark red during 20min) through the 5min color by blueness; When Tween-20 concentration was 40wt%, telltale began to change red (becoming dark red during 2h) through the 30min color by blueness; When Tween-20 concentration was 30wt%, telltale began to change red (becoming dark red during 48h) through the 2h color by blueness; When Tween-20 concentration was 20wt%, telltale began to change red (still being reddish brown during 48h) through the 24h color by blueness; When Tween-20 concentration was 15wt%, telltale began to change red (still being reddish brown during 48h) through the 48h color by blueness; When Tween-20 concentration during less than 15wt%, through also not variable color of 48h;
In the time of 30 ℃, when Tween-20 concentration is 50,40, during 30wt%, telltale begins to change red (becoming dark red during 5min) through the 5min color by blueness; When Tween-20 concentration was 20wt%, telltale began to change red (becoming dark red during 1h) through the 30min color by blueness; When Tween-20 concentration was 15wt%, telltale began to change red (becoming dark red during 2h) through the 1h color by blueness; When Tween-20 concentration was 10wt%, telltale began to change red (becoming dark red during 8h) through the 2h color by blueness; When Tween-20 concentration was 5wt%, telltale began to change red (still being reddish brown during 48h) through the 4h color by blueness; When Tween-20 concentration during less than 5wt%, through also not variable color of 48h;
In the time of 40 ℃, when Tween-20 concentration is 50,40,30,20,15,10, during 5wt%, telltale begins to change red (becoming dark red during 10min) through the 5min color by blueness; When Tween-20 concentration is 5, during 1wt%, telltale begins to change red (behind the 48h still for dark red) through the 2h color by blueness; When Tween-20 concentration during less than 1wt%, through also not variable color of 48h;
In the time of 50 ℃, when Tween-20 concentration was 0.5wt%, telltale began to change red (concentration became dark red greater than 1% o'clock during 5min) through the 5min color by blueness; When Tween-20 concentration during less than 0.5wt%, through also not variable color of 48h;
We can see by Fig. 5, and the colour-change of PDA/Tween-20 also obviously depends on the concentration of temperature, time and Tween-20; Although the molecular weight of Tween-20 is 1226, be lower than 1900 of L35, in the time of 10～30 ℃, the colour-change of PDA/Tween-20 shows tangible time-dependent manner; This just points out the molecular structure of amphipathic nature polyalcohol also the color of PDA/ amphipathic nature polyalcohol aqueous matrix to be had significant effects.
Embodiment
The invention provides a kind of time-temperature decolored indicator, it comprises gathers diacetylene (PDA) vesica and the amphipathic nature polyalcohol aqueous solution, and wherein, the PDA vesica is to be formed by diacetylene class material self-assembly post polymerization.
Wherein, above-mentioned amphipathic nature polyalcohol is selected from Bai Luoshamu, Tween-20 (Tween-20), Tween-80, TX10 (OP-10), a kind of in polycaprolactone-terepthaloyl moietie (PCL-PEG) or the Vinylpyrrolidone polymer (PVP); Wherein, Prist is the polyoxyethylene poly-oxygen propylene aether segmented copolymer.
Wherein, above-mentioned diacetylene class material is 10,12-tricosyl diacetylenic acid (PCDA), 2,4-heneicosyl diacetylenic acid (HCDA), 2,4-pentadecyl diacetylenic acid (PDDA) or 2,4-tricosyl diacetylenic acid (TCDA).
Preferably, the mean particle size of PDA vesica of the present invention is 80～300nm, the convenient preparation of the PDA vesica of this scope.
PDA vesica concentration of the present invention during to the PDA/ amphipathic nature polyalcohol aqueous solution time-temperature indicator monitoring articles colour-change influence little, the concentration of PDA gets final product in 0.05mg/mL-10mg/mL usually; This TTI is mainly along with the variation of the concentration of the amphipathic nature polyalcohol aqueous solution, its color to time-temperature produces response, the concentration preferable range that is suitable for the amphipathic nature polyalcohol of TTI in 0～50 ℃ of TR is 0.001～50wt% (weight percent).
The present invention has pointed out that also temperature variation and/or time that above-mentioned time-temperature decolored indicator is used to monitor in 0～50 ℃ of TR change.
Temperature and/or time that time-temperature indicator of the present invention can be used for monitoring in the perishable article transportation change, and the temperature and/or the time that are preferred for monitoring in vaccine, the biologics transportation change.Also can be used for monitoring of environmental temperature variation and/or time changes, like the temperature variation that is used for the monitoring experiment process in the scientific research and time changing conditions etc.
Time-temperature indicator of the present invention is used to indicate variation of ambient temperature and/or time to change or indicates monitored article to surpass suitable preservation condition; Be specially: need be controlled at 10 ℃ of reaction 30min down like a certain experiment; Can be that the Tween-20 blend of 50wt% is placed in this reaction environment when 5min (20 ℃ the time can variable color) with PDA vesica and concentration so; In case find this telltale variable color, show that then this reaction environment is in 20 ℃ and has surpassed 5min.Again for example: certain article such as vaccine will be preserved 24h down at 20 ℃; Can be that Tween-20 blend when 24h (20 ℃ the time can variable color), PDA vesica and the concentration of 20wt% is that L35 blend when 5min (30 ℃ the time can variable color), PDA vesica and the concentration of 40wt% is that Tween-20 blend when 1h (30 ℃ the time can variable color), PDA vesica and the concentration of 15wt% is that four kinds of telltales of F68 blend when 5min (40 ℃ the time can variable color) and the vaccine of 15wt% puts together with PDA vesica and concentration so; Variable color situation according to telltale; Can judge and live through which temperature-time history in the vaccine storage process; If PDA vesica and concentration are the F68 blend telltale variable color of 15wt%; Show that then living through 40 ℃ and this temperature in the storage has surpassed 5min, just can confirm optionally so so whether vaccine can continue use and still lose efficacy.
Again such as, meet accident in storage or the transportation, raise suddenly like the some time temperature, can redden in the monitoring thing color that has certain set to surpass this temperature generation colour-change in the telltale, explain that should not use has unusually appearred in this thing to be detected.If storage time is long, surpassed the quality guaranteed period of setting, then also have the historic records of certain time colour-change in the monitor, because this colour-change is irreversible.
The present invention also provides the method for use of above-mentioned time-temperature decolored indicator, and concrete steps are:
(1) it is subsequent use to dispose the amphipathic nature polyalcohol aqueous solution and the PDA vesica of desired concn respectively;
(2) with the amphipathic nature polyalcohol aqueous solution that configures and the blend of PDA vesica, blend and article put together;
(3) mixture colour-change indicative for environments temperature variation in the above-mentioned steps 2 and/or time change; Or indicate monitored article to surpass suitable temperature and/or the time of preserving.
Step 1 in the above-mentioned method of use can be selected the concentration of the amphipathic nature polyalcohol aqueous solution according to table 1-table 4 for use:
The concentration (wt%) of amphipathic nature polyalcohol during the following PDA/ amphipathic nature polyalcohol system variable color of 50 ℃ in table 1
Annotate: table 1 variable color is meant that PDA/ amphipathic nature polyalcohol water solution system becomes redness by the visible blueness, and following table together;
"/" representative in the table 1 in second row: when concentration during less than 0.5wt%, 50 ℃ of following PDA vesica/F127 mixtures all do not have variable color through 1h, 3h; "/" in the third line representative: when concentration during less than 10wt%, 50 ℃ of following PDA vesica/F68 mixtures all do not have variable color through 10min, 1h, 3h; The representative of "/" in the fourth line: when concentration during less than 5wt%, 50 ℃ of following PDA vesica/L35 mixtures all do not have variable color through 10min, 1h, 3h; The representative of "/" in the fifth line: when concentration during less than 0.5wt%, 50 ℃ of following PDA vesica/Tween-20 mixtures all do not have variable color through 10min, 1h, 3h.
The concentration (wt%) of amphipathic nature polyalcohol during the following PDA/ amphipathic nature polyalcohol system variable color of 40 ℃ in table 2
Figure BDA0000069854780000112
Annotate: "/" representative in the table 2 in second row: when concentration during less than 0.5wt%, 40 ℃ of following PDA vesica/F127 mixtures do not have variable color through 2h; "/" in the third line representative: when concentration during less than 15wt%, 40 ℃ of following PDA vesica/F68 mixtures all do not have variable color through 30min, 1h, 2h; The representative of "/" in the fourth line: when concentration during less than 10wt%, 40 ℃ of following PDA vesica/L35 mixtures all do not have variable color through 30min, 1h, 2h; The representative of "/" in the fifth line: when concentration during less than 5wt%, 40 ℃ of following PDA vesica/Tween-20 mixtures all do not have variable color through 30min, 1h, 2h.
The concentration (wt%) of amphipathic nature polyalcohol during the following PDA/ amphipathic nature polyalcohol system variable color of 30 ℃ in table 3
Figure BDA0000069854780000122
Annotate: "/" representative in the table 3 in second row: when concentration during less than 10wt%, 30 ℃ of following PDA vesica/F127 mixtures all do not have variable color through 1h, 2h; "/" in the third line representative: when concentration during less than 30wt%, 30 ℃ of following PDA vesica/F68 mixtures all do not have variable color through 30min, 1h, 2h, 4h; The representative of "/" in the fourth line: when concentration during less than 40wt%, 30 ℃ of following PDA vesica/L35 mixtures all do not have variable color through 30min, 1h, 2h, 4h;
"-" expression " is surveyed " in the table, and following table together.
The concentration (wt%) of amphipathic nature polyalcohol during the following PDA/ amphipathic nature polyalcohol system variable color of 20 ℃ in table 4
Annotate: "/" representative in the table 4 in second row: when concentration during less than 15wt%, 20 ℃ of following PDA vesica/F127 mixtures do not have variable color through 24h; The representative respectively of "/" in the fifth line: when concentration during less than 40wt%, 20 ℃ of following PDA vesica/Tween-20 mixtures do not have variable color through 1h; And when concentration during less than 30wt%, 20 ℃ of following PDA vesica/Tween-20 mixtures pass through 4h does not have variable color.
In addition, being used to monitor 10 ℃ of time-temperature indicators of preserving the article that are no more than 2h down is: PDA vesica and concentration are the Tween-20 blend of 40wt%; Being used to monitor 10 ℃ of time-temperature indicators of preserving the article that are no more than 30min down is: PDA vesica and concentration are the Tween-20 blend of 50wt%.Being used to monitor 0 ℃ of time-temperature indicator of preserving the article that are no more than 48h down is: PDA vesica and concentration are the Tween-20 blend of 50wt%;
Because of monomeric alkynyl one side of diine connects long chain alkane; The alkane chain end of opposite side is a polar group; So be similar to amphiphilic, the diine monomer can self-assembly in water, forms to have double-deck vesica; Through the ultraviolet lighting polymerization, make original vesica have higher physical strength again.Gathering diacetylene (PDA) is a kind of pi-conjugated polymkeric substance, and two keys and triple bond alternately occur generally demonstrating blueness in the main polymer chain; Usually, the PDA vesica is blue below 50oC, when temperature meets or exceeds about 60oC, can become redness (because PDA vesica fusing point is 61oC) by blueness in a short period of time.In addition, from the above, the PDA vesica has hydrophobic section and hydrophilic section.
And the material of amphipathic nature polyalcohol while possess hydrophilic property group and oleophilicity group, such as Bai Luoshamu, a kind of PEG-PPG-PEG triblock copolymer; Its oleophilicity group can be inserted in the lipid unimolecular layer on above-mentioned PDA vesica surface; Along with temperature or change of time, be inserted into the oleophilicity group of the APP in the surperficial lipid unimolecular layer of above-mentioned vesica and the hydrophobic part generation hydrophobic interaction among the PDA, change the conformation of PDA; Thereby cause the variable color of PDA, become redness by blueness.Therefore, PDA vesica and amphipathic nature polyalcohol mixture be along with the variation of temperature and time, will produce macroscopicly to become redness by blueness, and this variable color is irreversible; It is thus clear that the PDA/ amphipathic nature polyalcohol can be used as time-temperature indicator, monitor the time-temperature history in the perishables conveyer chains such as vaccine.
Below through the form of specific embodiment the present invention is done further detailed description, be limitation of the present invention but should not be construed as.
Embodiment 1 monitoring condition of storage is 40 ℃ of following article of 1 hour
1, the preparation of PDA vesica and sign
40 milligrams of PCDA are dissolved in CH 2Cl 2, subsequently solvent is volatilized, add 20 ml waters after, under 75 ℃ temperature, ultrasonic 10 minutes.Cooling then 4 ℃ of preservations of spending the night, makes fat property membrane crystallization.Polyreaction was carried out in ice bath 5 minutes under 254nm wavelength UV-irradiation.At last, the PDA vesica that obtains be kept at 4 ℃ subsequent use.Through the laser particle analyzer test, the mean particle size of PDA vesica is 128.5 ± 4.8nm.The result is the MV of three tests.
2, the preparation of the F127 aqueous solution
Preparation concentration is the F127 aqueous solution of 0.5wt%.The molecular structure of F127 is PEG99-PPG67-PEG99, and molecular weight is 12700.
3, utilize the article of PDA vesica/40 ℃ of following variable colors in following 1 hour of F127 monitoring
With the PDA vesica for preparing and concentration is that the F127 solution of 0.5wt% places independent collecting bottle respectively, when article delivery to be monitored, the PDA vesica divided mixes with the F127 of 0.5wt%, with mixture with need put together by conveying objects, deliver; When arriving this conveyer chain terminal, change, when promptly becoming redness, explain to surpass storing temp, the time of setting that anorexia is used or used by blueness if find certain PDA vesica/F127 mixture color.
Embodiment 2 monitoring conditions of storage are 20 ℃ of following article of 4 hours
Change the preparation concentration of F127 among the embodiment 1 into 15wt%, replace PCDA to prepare the PDA vesica with HCDA, other steps are with embodiment 1.
When article to be monitored delivery, be that 15% F127 mixes with PDA vesica and concentration, mixture and need conveying objects are put together, deliver; When arriving this conveyer chain terminal, change, when promptly becoming redness, explain to surpass storing temp, the time of setting that anorexia is used or used by blueness if find certain PDA vesica/F127 mixture color.
Embodiment 3 monitoring conditions of storage are following 2 days of 20 degree temperature
With replacing PCDA to prepare the PDA vesica with PDDA among the embodiment 1, replace F127 with Tween-20, preparation concentration is the Tween-20 solution of 15wt%, other steps are with embodiment 1.
It is the following 2 days article of 20 degree temperature that PDA/Tween-20 (concentration is 15wt%) is used to monitor condition of storage: when article to be monitored are delivered; With PDA vesica and concentration is that 15% Tween-20 mixes; Mixture is put together with needing conveying objects; Delivery in order to guarantee accuracy, can be placed many group mixtures simultaneously; When arriving this conveyer chain terminal, change, when promptly becoming redness, explain to surpass storing temp, the time of setting that anorexia is used or used by blueness if find certain PDA vesica/Tween-20 mixture color.
Embodiment 4 monitoring conditions of storage are following 1 day of 20 temperature
With replacing PCDA to prepare the PDA vesica with TCDA among the embodiment 1, replace F127 with Tween-20, preparation concentration is the Tween-20 solution of 25wt%, other steps are with embodiment 1.
It is the following 1 day article of 20 degree temperature that PDA/Tween-20 (concentration is 20wt%) is used to monitor condition of storage: when article to be monitored are delivered; With PDA vesica and concentration is that 20% Tween-20 mixes; Mixture is put together with needing conveying objects; Delivery in order to guarantee accuracy, can be placed many group mixtures simultaneously; When arriving this conveyer chain terminal, change, when promptly becoming redness, explain to surpass storing temp, the time of setting that anorexia is used or used by blueness if find certain PDA vesica/Tween-20 mixture color.
The molecular structure of above-mentioned F127 is PEG 99-PPG 67-PEG 99, molecular weight is 12700; The molecular structure of F68 is PEG 76-PPG 29-PEG 76, M n=8400; The molecular structure of L35 is PEG 11-PPG 16-PEG 11, M n=1900.
Concrete use that time-temperature history is not limited to the foregoing description in the time-temperature indicator monitoring articles conveyer chain of the present invention, can according in the table 1 time-temperature variation point selects PDA vesica and amphipathic nature polyalcohol flexibly for use; Use-pattern also is not limited only to two kinds of materials of the independent splendid attire of elder generation that embodiment mentions; Can design as adopting a kind of box that has some locellus; Difference splendid attire PDA and amphipathic nature polyalcohol solution; Treat to take out out when article are about to transport the locellus baffle plate PDA and amphipathic nature polyalcohol solution are mixed, monitor the temperature-time changing conditions of corresponding perishable prod.In addition, temperature variation and/or time that time-temperature indicator of the present invention can also be used to monitoring in 0～50 ℃ of TR change, like the temperature variation that is used for the monitoring experiment process in the scientific research and time changing conditions etc.

Claims (10)

  1. Time-the temperature decolored indicator, it is characterized in that, comprise the PDA vesica and the amphipathic nature polyalcohol aqueous solution; Wherein, the PDA vesica is to be formed by the diacetylene class material self-assembly post polymerization shown in the formula I, and the PDA vesica is by shown in the formula II:
    Figure FDA0000069854770000011
    M is 5～500, and n is 5～500, and preferred m is 10～20, and n is 3～10;
    Wherein, R is a hydrophilic radical, said hydrophilic radical contains-COOH ,-NH 2Or-OH; R ' is a hydrophobic grouping, and said hydrophobic grouping contains:
    -CH 2、
    Figure FDA0000069854770000012
    x＝1～10、
    Figure FDA0000069854770000013
  2. 2. time according to claim 1-temperature decolored indicator, it is characterized in that: said amphipathic nature polyalcohol is Bai Luoshamu, Tween-20, Tween-80, OP-10, PCL-PEG or PVP; Said diacetylene class material is 10,12-tricosyl diacetylenic acid, 2,4-heneicosyl diacetylenic acid, 2,4-pentadecyl diacetylenic acid or 10,12-tricosyl diacetylenic acid.
  3. 3. time according to claim 1 and 2-temperature decolored indicator, it is characterized in that: the concentration of the said amphipathic nature polyalcohol aqueous solution is 0.001～50wt%.
  4. 4. the application that changes of temperature variation and/or the time of each described time of claim 1-3-temperature decolored indicator in 0～50 ℃ of TR of monitoring.
  5. 5. the application that changes of temperature variation and/or the time of described time of claim 4-temperature decolored indicator in 0～50 ℃ of TR of monitoring; It is characterized in that the temperature and/or the time that are used for monitoring in perishable article transportation or the storage process change.
  6. 6. the application that changes of temperature variation and/or the time of described time of claim 5-temperature decolored indicator in 0～50 ℃ of TR of monitoring; It is characterized in that the temperature and/or the time that are used for monitoring in vaccine, biologics transportation or the storage process change.
  7. 7. the application that changes according to temperature variation and/or the time of each described time of claim 4-6-temperature decolored indicator in 0～50 ℃ of TR of monitoring is characterized in that:
    Being used for monitoring 50 ℃ of time-temperature indicators of preserving the article that are no more than 5min down is selected from: PDA vesica and concentration are that F127 blend, PDA vesica and the concentration of 2wt% is that F68 blend, PDA vesica and the concentration of 10wt% is that L35 blend, PDA vesica and the concentration of 5wt% is Tween-20 blend at least a of 0.5wt%; Or
    Being used to monitor 50 ℃ of time-temperature indicators of preserving the article that are no more than 10min down is: PDA vesica and concentration are the F127 blend of 0.5wt%; Or
    Being used to monitor 40 ℃ of time-temperature indicators of preserving the article that are no more than 1h down is: PDA vesica and concentration are the F127 blend of 0.5wt%; Or
    Being used to monitor 40 ℃ of time-temperature indicators of preserving the article that are no more than 30min down is: PDA vesica and concentration are the F127 blend of 2wt%; Or
    Being used for monitoring 40 ℃ of time-temperature indicators of preserving the article that are no more than 5min down is selected from: PDA vesica and concentration are that F127 blend, PDA vesica and the concentration of 10wt% is that F68 blend, PDA vesica and the concentration of 15wt% is that L35 blend, PDA vesica and the concentration of 10wt% is Tween-20 blend at least a of 5wt%; Or
    Being used for monitoring 30 ℃ of time-temperature indicators of preserving the article that are no more than 4h down is: PDA vesica and concentration are that F127 blend, PDA vesica and the concentration of 5wt% is Tween-20 blend at least a of 5wt%; Or
    Being used to monitor 30 ℃ of time-temperature indicators of preserving the article that are no more than 2h down is: PDA vesica and concentration are the Tween-20 blend of 15wt%; Or
    Being used to monitor 30 ℃ of time-temperature indicators of preserving the article that are no more than 1h down is: PDA vesica and concentration are the Tween-20 blend of 10wt%; Or
    Being used for monitoring 30 ℃ of time-temperature indicators of preserving the article that are no more than 30min down is selected from: PDA vesica and concentration are that F127 blend, PDA vesica and the concentration of 10wt% is Tween-20 blend at least a of 20wt%; Or
    Being used for monitoring 30 ℃ of time-temperature indicators of preserving the article that are no more than 5min down is selected from: PDA vesica and concentration are that F68 blend, PDA vesica and the concentration of 30wt% is that L35 blend, PDA vesica and the concentration of 40wt% is Tween-20 blend at least a of 30wt%; Or
    Being used to monitor 20 ℃ of time-temperature indicators of preserving the article that are no more than 48h down is: PDA vesica and concentration are the Tween-20 blend of 15wt%; Or
    Being used to monitor 20 ℃ of time-temperature indicators of preserving the article that are no more than 24h down is: PDA vesica and concentration are the Tween-20 blend of 20wt%; Or
    Being used to monitor 20 ℃ of time-temperature indicators of preserving the article that are no more than 4h down is: PDA vesica and concentration are the F127 blend of 15wt%; Or
    Being used for monitoring 20 ℃ of time-temperature indicators of preserving the article that are no more than 2h down is selected from: PDA vesica and concentration are that F127 blend, PDA vesica and the concentration of 20wt% is Tween-20 blend at least a of 30wt%; Or
    Being used for monitoring 20 ℃ of time-temperature indicators of preserving the article that are no more than 30min down is selected from: PDA vesica and concentration are that F68 blend, PDA vesica and the concentration of 40wt% is Tween-20 blend at least a of 40wt%; Or
    Being used to monitor 20 ℃ of time-temperature indicators of preserving the article that are no more than 5min down is: PDA vesica and concentration are the Tween-20 blend of 50wt%; Or
    Being used to monitor 10 ℃ of time-temperature indicators of preserving the article that are no more than 4h down is: PDA vesica and concentration are the Tween-20 blend of 40wt%; Or
    Being used to monitor 10 ℃ of time-temperature indicators of preserving the article that are no more than 30min down is: PDA vesica and concentration are the Tween-20 blend of 50wt%; Or
    Being used to monitor 0 ℃ of time-temperature indicator of preserving the article that are no more than 48h down is: PDA vesica and concentration are the Tween-20 blend of 50wt%.
  8. 8. the application that changes according to temperature variation and/or the time of each described time of claim 4-6-temperature decolored indicator in 0～50 ℃ of TR of monitoring is characterized in that:
    (1) a, b, c, four kinds of time-temperature indicators of d and article put together the temperature variation of article in the monitoring 5min, wherein:
    The a telltale is selected from: PDA vesica and concentration are that F127 blend, PDA vesica and the concentration of 2wt% is that F68 blend, PDA vesica and the concentration of 10wt% is that L35 blend, PDA vesica and the concentration of 5wt% is at least a in the Tween-20 blend of 0.5wt%;
    The b telltale is selected from: PDA vesica and concentration are that F127 blend, PDA vesica and the concentration of 10wt% is that F68 blend, PDA vesica and the concentration of 15wt% is that L35 blend, PDA vesica and the concentration of 10wt% is at least a in the Tween-20 blend of 5wt%;
    The c telltale is selected from: PDA vesica and concentration are that F68 blend, PDA vesica and the concentration of 30wt% is that L35 blend, PDA vesica and the concentration of 40wt% is at least a in the Tween-20 blend of 30wt%;
    The d telltale is that PDA vesica and concentration are the Tween-20 blend of 50wt%; Or
    (2) e, two kinds of time-temperature indicators of f and article put together the temperature variation of article in the monitoring 10min, wherein:
    The e telltale is that PDA vesica and concentration are the F127 blend of 0.5wt%;
    The f telltale is that PDA vesica and concentration are the Tween-20 blend of 10wt%; Or
    (3) g, h, i, four kinds of time-temperature indicators of j and article put together the temperature variation of article in the monitoring 30min, wherein:
    The g telltale is that PDA vesica and concentration are the F127 blend of 2wt%;
    The h telltale is selected from: PDA vesica and concentration are that F127 blend, PDA vesica and the concentration of 10wt% is at least a in the Tween-20 blend of 20wt%;
    The i telltale is selected from: PDA vesica and concentration are that F68 blend, PDA vesica and the concentration of 40wt% is at least a in the Tween-20 blend of 40wt%;
    The j telltale is that PDA vesica and concentration are the Tween-20 blend of 50wt%; Or
    (4) k, l, three kinds of time-temperature indicators of m and article put together the temperature variation of article in the monitoring 4h, wherein:
    The k telltale is selected from: PDA vesica and concentration are that F127 blend, PDA vesica and the concentration of 5wt% is at least a in the Tween-20 blend of 5wt%;
    The l telltale is: PDA vesica and concentration are the F127 blend of 15wt%;
    The m telltale is: PDA vesica and concentration are the Tween-20 blend of 40wt%; Or
    N, two kinds of time-temperature indicators of o and article put together the temperature variation of article in the monitoring 2h, wherein:
    The n telltale is: PDA vesica and concentration are the Tween-20 blend of 15wt%;
    The o telltale is selected from: PDA vesica and concentration are that F127 blend, PDA vesica and the concentration of 20wt% is at least a in the Tween-20 blend of 30wt%.
  9. 9. be used to monitor 0～50 ℃ of temperature variation and/or time in the TR according to each described time of claim 4-6-temperature decolored indicator and change, it is characterized in that:
    (1) time of article changed in A, two kinds of time-temperature indicators of B and article put together and monitor 50 ℃, wherein:
    The A telltale is selected from: PDA vesica and concentration are that F127 blend, PDA vesica and the concentration of 2wt% is that F68 blend, PDA vesica and the concentration of 10wt% is that L35 blend, PDA vesica and the concentration of 5wt% is at least a in the Tween-20 blend of 0.5wt%;
    The B telltale is: PDA vesica and concentration are the F127 blend of 0.5wt%; Or
    (2) time of article changed in C, D, three kinds of time-temperature indicators of E and article put together and monitor 40 ℃, wherein:
    The C telltale is: PDA vesica and concentration are the F127 blend of 0.5wt%;
    The D telltale is: PDA vesica and concentration are the F127 blend of 2wt%;
    The E telltale is selected from: PDA vesica and concentration are that F127 blend, PDA vesica and the concentration of 10wt% is that F68 blend, PDA vesica and the concentration of 15wt% is that L35 blend, PDA vesica and the concentration of 10wt% is at least a in the Tween-20 blend of 5wt%; Or
    (3) time of article changed in F, G, H, I, five kinds of time-temperature indicators of J and article put together and monitor 30 ℃, wherein:
    The F telltale is selected from: PDA vesica and concentration are that F127 blend, PDA vesica and the concentration of 5wt% is at least a in the Tween-20 blend of 5wt%;
    The G telltale is: PDA vesica and concentration are the Tween-20 blend of 15wt%;
    The H telltale is: PDA vesica and concentration are the Tween-20 blend of 10wt%;
    The I telltale is selected from: PDA vesica and concentration are that F127 blend, PDA vesica and the concentration of 10wt% is at least a in the Tween-20 blend of 20wt%;
    The J telltale is selected from: PDA vesica and concentration are that F68 blend, PDA vesica and the concentration of 30wt% is that L35 blend, PDA vesica and the concentration of 40wt% is at least a in the Tween-20 blend of 30wt%; Or
    (4) time of article changed in K, L, M, N, O, six kinds of time-temperature indicators of P and article put together and monitor 20 ℃, wherein:
    The K telltale is: PDA vesica and concentration are the Tween-20 blend of 15wt%;
    The L telltale is: PDA vesica and concentration are the Tween-20 blend of 20wt%;
    The M telltale is: PDA vesica and concentration are the F127 blend of 15wt%;
    The N telltale is selected from: PDA vesica and concentration are that F127 blend, PDA vesica and the concentration of 20wt% is at least a in the Tween-20 blend of 30wt%;
    The O telltale is selected from: PDA vesica and concentration are that F68 blend, PDA vesica and the concentration of 40wt% is at least a in the Tween-20 blend of 40wt%;
    The P telltale is: PDA vesica and concentration are the Tween-20 blend of 50wt%; Or
    (5) time of article changed in Q, two kinds of time-temperature indicators of R and article put together and monitor 10 ℃, wherein:
    The Q telltale is: PDA vesica and concentration are the Tween-20 blend of 40wt%;
    The R telltale is: PDA vesica and concentration are the Tween-20 blend of 50wt%.
  10. 10. the method for use of each described time of claim 1-9-temperature decolored indicator, concrete steps are:
    (1) it is subsequent use to dispose the amphipathic nature polyalcohol aqueous solution and the PDA vesica of desired concn respectively;
    (2) with the amphipathic nature polyalcohol aqueous solution that configures and the blend of PDA vesica, blend and article put together;
    (3) mixture colour-change indicative for environments temperature variation in the above-mentioned steps 2 and/or time change; Or indicate monitored article to surpass suitable temperature and/or the time of preserving.
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CN104330188A (en) * 2014-11-25 2015-02-04 胡浩 One-time over-temperature detecting method
CN106197734A (en) * 2016-07-04 2016-12-07 广西大学 Use Crusta Penaeus seu Panulirus as the method for time temperature indicator
US9816870B2 (en) 2012-06-21 2017-11-14 Weimin Huang Temperature indicating method, temperature indicating label and method for manufacturing the label
CN110672596A (en) * 2019-10-14 2020-01-10 军事科学院军事医学研究院环境医学与作业医学研究所 Colorimetric strip for quickly detecting histamine, colorimetric card and detection method
CN111982336A (en) * 2020-08-26 2020-11-24 中国烟草总公司郑州烟草研究院 Tobacco hot processing strength detection method based on temperature-sensitive marker
CN113532683A (en) * 2021-07-09 2021-10-22 江南大学 Time temperature indicator based on polydiacetylene liposome and preparation method thereof
CN114957706A (en) * 2022-05-24 2022-08-30 四川大学华西医院 Vesicle with stability and permeability as well as preparation method and application thereof

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US9816870B2 (en) 2012-06-21 2017-11-14 Weimin Huang Temperature indicating method, temperature indicating label and method for manufacturing the label
CN104267163A (en) * 2014-09-04 2015-01-07 江苏省农业科学院 Food storage life indicator, preparation method and inspection method thereof
CN104330188A (en) * 2014-11-25 2015-02-04 胡浩 One-time over-temperature detecting method
CN104330188B (en) * 2014-11-25 2017-10-03 胡浩 One kind is disposable to cross temperature detection method
CN106197734A (en) * 2016-07-04 2016-12-07 广西大学 Use Crusta Penaeus seu Panulirus as the method for time temperature indicator
CN110672596A (en) * 2019-10-14 2020-01-10 军事科学院军事医学研究院环境医学与作业医学研究所 Colorimetric strip for quickly detecting histamine, colorimetric card and detection method
CN110672596B (en) * 2019-10-14 2022-02-22 军事科学院军事医学研究院环境医学与作业医学研究所 Colorimetric strip for quickly detecting histamine, colorimetric card and detection method
CN111982336A (en) * 2020-08-26 2020-11-24 中国烟草总公司郑州烟草研究院 Tobacco hot processing strength detection method based on temperature-sensitive marker
CN111982336B (en) * 2020-08-26 2022-05-20 中国烟草总公司郑州烟草研究院 Tobacco hot processing strength detection method based on temperature-sensitive marker
CN113532683A (en) * 2021-07-09 2021-10-22 江南大学 Time temperature indicator based on polydiacetylene liposome and preparation method thereof
CN114957706A (en) * 2022-05-24 2022-08-30 四川大学华西医院 Vesicle with stability and permeability as well as preparation method and application thereof
CN114957706B (en) * 2022-05-24 2024-03-12 四川大学华西医院 Vesicle with stability and permeability as well as preparation method and application thereof

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