CN102336996B - 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 PDFInfo
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- CN102336996B CN102336996B CN201110167000.7A CN201110167000A CN102336996B CN 102336996 B CN102336996 B CN 102336996B CN 201110167000 A CN201110167000 A CN 201110167000A CN 102336996 B CN102336996 B CN 102336996B
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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
Technical field
The present invention relates to a kind of time-temperature color-changing indicator, particularly based on the time-temperature color-changing indicator of poly-diacetylene, belong to the technical field of the transportations such as monitoring food, vaccine.
Background technology
The quality height of food and other perishable prod (such as fresh foods prods, vaccine, some medicine etc.) depends on storage requirement and transport condition, as from produce or packing until conditions such as the temperature in during its last this section of the ultimate consumer of arrival and storage times, elongated along with the rising of temperature and time, because the increase of biochemical reaction speed, so that the deterioration process is accelerated; Therefore, need in these Product transport processes to store under the condition that is no more than the specified temp restriction, perhaps period of storage can not exceed the predetermined time interval at least.
Current, general only guarantee the quality of storing with date stamp, and only use date stamp, in fact can't provide the information of the storage requirement that has exposed therein about this product to human consumer or other people.For example, certain food is demarcated as 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 that this based food stores 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, the normal operation time-temperature indicator is monitored the real shelf-life of every product, time temperature indicator (TTI) is defined as a kind of easy device, can present 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-temperature indicator, comprising a kind of meltability material, for example polycaprolactone triol, macrogol C1-4 alkyl oxide and polyvinyl alcohol, 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 at a substrate, and when the meltability material flows therein, and indicator system is just in a kind of variation that can detect with physical method of substrate generation.
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 time-temperature color-changing indicator (TTI) that is suitable in 0～50 ℃ of temperature range, the temperature variation and/or the time that are used for the perishable object storing such as monitoring 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 (poly-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 that 5～500, n is 5～500; Preferred m is that 10～20, n is 3～10;
In the formula, R is hydrophilic radical, and described hydrophilic radical contains-COOH ,-NH
2Or-OH; R ' is hydrophobic grouping, and described hydrophobic grouping contains:
-CH
2，
x＝1～10，
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 temperature variation of above-mentioned time-temperature color-changing indicator in 0～50 ℃ of temperature range of monitoring and/or the application of time variation.
Temperature and/or time that time-temperature indicator of the present invention can be used for monitoring in the perishable goods transportation process 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 50 ℃ of lower time-temperature indicators of preserving the article that are no more than 5min of monitoring 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 for 50 ℃ of lower time-temperature indicators of preserving the article that are no more than 10min of monitoring is: PDA vesica and concentration are the F127 blend of 0.5wt%; Or
Being used for 40 ℃ of lower time-temperature indicators of preserving the article that are no more than 1h of monitoring is: PDA vesica and concentration are the F127 blend of 0.5wt%; Or
Being used for 40 ℃ of lower time-temperature indicators of preserving the article that are no more than 30min of monitoring is: PDA vesica and concentration are the F127 blend of 2wt%; Or
Being used for 40 ℃ of lower time-temperature indicators of preserving the article that are no more than 5min of monitoring 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 30 ℃ of lower time-temperature indicators of preserving the article that are no more than 4h of monitoring 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 for 30 ℃ of lower time-temperature indicators of preserving the article that are no more than 2h of monitoring is: PDA vesica and concentration are the Tween-20 blend of 15wt%; Or
Being used for 86 °F of lower time-temperature indicators of preserving the article that are no more than 1h of monitoring is: PDA vesica and concentration are the Tween-20 blend of 10wt%; Or
Being used for 30 ℃ of lower time-temperature indicators of preserving the article that are no more than 30min of monitoring 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 30 ℃ of lower time-temperature indicators of preserving the article that are no more than 5min of monitoring 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 for 20 ℃ of lower time-temperature indicators of preserving the article that are no more than 48h of monitoring is: PDA vesica and concentration are the Tween-20 blend of 15wt%; Or
Being used for 20 ℃ of lower time-temperature indicators of preserving the article that are no more than 24h of monitoring is: PDA vesica and concentration are the Tween-20 blend of 20wt%; Or
Being used for 20 ℃ of lower time-temperature indicators of preserving the article that are no more than 4h of monitoring is: PDA vesica and concentration are the F127 blend of 15wt%; Or
Being used for 20 ℃ of lower time-temperature indicators of preserving the article that are no more than 2h of monitoring 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 20 ℃ of lower time-temperature indicators of preserving the article that are no more than 30min of monitoring 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 for 20 ℃ of lower time-temperature indicators of preserving the article that are no more than 5min of monitoring is: PDA vesica and concentration are the Tween-20 blend of 50wt%; Or
Being used for 10 ℃ of lower time-temperature indicators of preserving the article that are no more than 4h of monitoring is: PDA vesica and concentration are the Tween-20 blend of 40wt%; Or
Being used for 10 ℃ of lower time-temperature indicators of preserving the article that are no more than 30min of monitoring 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, four kinds of time-temperature indicators of c, 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
Two kinds of time-temperature indicators of e, 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, four kinds of time-temperature indicators of i, 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
Two kinds of time-temperature indicators of n, 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 two kinds of time-temperature indicators of A, 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, six kinds of time-temperature indicators of O, 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 two kinds of time-temperature indicators of Q, 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 using method of above-mentioned time-temperature color-changing indicator, and concrete steps are:
(1) it is for subsequent use to dispose respectively the amphipathic nature polyalcohol aqueous solution and the PDA vesica of desired concn;
(2) with the amphipathic nature polyalcohol aqueous solution and the blend of PDA vesica that configure, blend and article put together;
(3) the 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: the preparation synoptic diagram of the time-temperature color-changing indicator of PDA vesica and amphipathic nature polyalcohol.
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 quantitative assay PDA/F127 telltale.In order quantitatively to determine color from indigo plant to red intensity of variation, available following formula quantitative Analysis CR:CR (%)=[(PB
0-PB
1)/PB
0] * 100; Specifically the 0.15mL sample is joined in 96 orifice plates, with the absorbance value of the quick test of spectrophotometer (M5, Molecular Corporation) at 640nm and 550nm.
PB=A wherein
Blue/ (A
Blue+ A
Red).
A is the absorption value in blue (640nm) or red (550nm) component;
PB
0The blue ratio of pure PDA liquid under 0 degree, in 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 by 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 jointly causes PDA, thus colour-change occurs; 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 is along with the variation (0.1-20wt%) of F127 concentration did not all occur macroscopic from indigo plant to red colour-change through 3 days with 24h respectively;
In the time of 20 ℃, when F127 concentration is 20wt%, begin to turn red by blueness through the 2h telltale, along with the prolongation color of time becomes dark red (becoming redness fully such as the 24h color) by reddish brown; When F127 concentration is 15wt%, begin to turn red by blueness through the 4h telltale, 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 turn red by blueness through the 30min telltale, along with the prolongation color of time becomes dark red (becoming redness fully such as color behind the 2h) by reddish brown; When F127 concentration is 5wt%, begin to turn red by blueness through the 4h telltale, along with the prolongation color of time becomes dark red (becoming redness fully such as color behind the 24h) by reddish brown; 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 turn red by blueness through the 5min telltale, along with the prolongation color of time becomes dark red (becoming redness fully such as color behind the 30min) by reddish brown; When F127 concentration is 2wt%, begin to turn red by blueness through the 30min telltale, along with the prolongation color of time becomes dark red (becoming redness fully such as color behind the 1h) by reddish brown; When F127 concentration is 0.5wt%, begin to turn red by blueness through the 1h telltale, along with the prolongation color of time becomes dark red (becoming redness fully such as color behind the 8h) by reddish brown; 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 turn red by blueness through the 5min telltale, along with the prolongation color of time becomes dark red (becoming redness fully such as color behind the 10min) by reddish brown; When F127 concentration is 1, during 0.5wt%, begin to turn red by blueness through the 10min telltale, along with the prolongation color of time becomes dark red (becoming redness fully such as color behind the 15min) by reddish brown; When F127 concentration is 0.2, during 0.1wt%, begin to turn red by blueness through the 15min telltale, along with the prolongation color of time becomes dark red (becoming redness fully such as 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 higher, and the color transition temperature is lower, and color transition speed is faster; Simultaneously, temperature is higher, and color transition is faster.
As shown in Figure 3: quantitative analysis the color transition of PDA/F127, remain on 20%, CR along with the increase of the growth of time and temperature when the concentration of F127 and increase that (Fig. 3 is a); Remain 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 may become a kind of potential significant time-temperature color-changing indicator.
Shown in Fig. 4 (a):
Under 0 ℃, 10 ℃, the PDA/F68 telltale is along with the variation (0.1-40wt%) of F68 concentration did not occur macroscopic from indigo plant to red colour-change yet through 3 days;
In the time of 20 ℃, when F68 concentration is 40wt%, begin to turn red by blueness through the 30min telltale, along with the prolongation color of time becomes dark red (when lasting 48h still for reddish brown) by reddish brown; 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 turn red by blueness through the 5min telltale, along with the prolongation color of time becomes dark red (becoming redness fully such as 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 turn red by blueness through the 5min telltale, along with the prolongation color of time by reddish brown become dark red (as concentration greater than 15% the time behind the 5min color become redness fully); 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 turn red by blueness through the 5min telltale, along with the prolongation color of time by reddish brown become dark red (as concentration greater than 10% the time behind the 5min color become redness fully); 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 is along with the variation (0.1-40wt%) of L35 concentration does not occur macroscopic from indigo plant to red colour-change through 3 days, 3 days, 48h respectively yet;
In the time of 30 ℃, when L35 concentration is 40wt%, begin to turn red by blueness through the 5min telltale, along with the prolongation color of time becomes dark red (still being red-brown through 48h) by reddish brown; 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 turn red by blueness through the 5min telltale, along with the prolongation color of time by reddish brown become dark red (as concentration greater than 25% the time behind the 5min color become redness fully); 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 turn red by blueness through the 5min telltale, along with the prolongation color of time by reddish brown become dark red (as concentration greater than 5% the time behind the 5min color become redness fully); 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 on the color impact of PDA vesica the colour-change of visible temperature, polymer concentration dependence can both occur for PDA/F68 and PDA/L35, and polymer concentration is higher, and the color transition temperature is lower; From PDA/F127 to PDA/F68 to PDA/L35, the time-dependent manner of color transition progressively weakens, and this may be inserted among the PDA because of PEG-PPG-PEG relevant with molecular weight, and molecular weight is larger, the speed that is inserted among the PDA is slower, thereby the colour-change of PDA is also slower.
As shown in Figure 5:
Under 0 ℃, when Tween-20 concentration was 50wt%, the PDA/Tween-20 telltale began to turn red through the 48h color by blueness;
In the time of 10 ℃, when Tween-20 concentration was 40wt%, telltale began to turn red through the 4h color by blueness; When Tween-20 concentration was 50wt%, telltale began to turn 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 turn red (becoming dark red during 20min) through the 5min color by blueness; When Tween-20 concentration was 40wt%, telltale began to turn red (becoming dark red during 2h) through the 30min color by blueness; When Tween-20 concentration was 30wt%, telltale began to turn red (becoming dark red during 48h) through the 2h color by blueness; When Tween-20 concentration was 20wt%, telltale began to turn red (still being reddish brown during 48h) through the 24h color by blueness; When Tween-20 concentration was 15wt%, telltale began to turn 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 turn red (becoming dark red during 5min) through the 5min color by blueness; When Tween-20 concentration was 20wt%, telltale began to turn red (becoming dark red during 1h) through the 30min color by blueness; When Tween-20 concentration was 15wt%, telltale began to turn red (becoming dark red during 2h) through the 1h color by blueness; When Tween-20 concentration was 10wt%, telltale began to turn red (becoming dark red during 8h) through the 2h color by blueness; When Tween-20 concentration was 5wt%, telltale began to turn 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 turn red (becoming dark red during 10min) through the 5min color by blueness; When Tween-20 concentration is 5, during 1wt%, telltale begins to turn 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 turn red (concentration becomes dark red greater than 1% the time 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 obvious 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 important impact.
Embodiment
The invention provides a kind of time-temperature color-changing indicator, it comprises poly-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, alkylphenol polyoxyethylene (OP-10), a kind of in polycaprolactone-ethylene glycol (PCL-PEG) or the polyvinylpyrrolidone (PVP); Wherein, poloxamer 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 on the PDA/ amphipathic nature polyalcohol aqueous solution time-temperature indicator monitoring articles colour-change impact little, the concentration of PDA gets final product in 0.05mg/mL-10mg/mL usually; Mainly along with the variation of the concentration of the amphipathic nature polyalcohol aqueous solution, its color produces response to Time-temperature to this TTI, and the concentration preferable range that is suitable for the amphipathic nature polyalcohol of TTI in 0～50 ℃ of temperature range is 0.001～50wt% (weight percent).
The present invention has pointed out that also temperature variation and/or time that above-mentioned time-temperature color-changing indicator is used in 0～50 ℃ of temperature range of monitoring change.
Temperature and/or time that time-temperature indicator of the present invention can be used for monitoring in the perishable goods transportation process 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, such as 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 the time changes or indicate monitored article to surpass suitable preservation condition, be specially: need be controlled at 10 ℃ of lower reaction 30min such as 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) so with PDA vesica and concentration, 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 at 20 ℃ of lower 24h that preserve, can be Tween-20 blend when 24h (20 ℃ the time can variable color) of 20wt% so with PDA vesica and concentration, PDA vesica and concentration are L35 blend when 5min (30 ℃ the time can variable color) of 40wt%, PDA vesica and concentration are Tween-20 blend when 1h (30 ℃ the time can variable color) of 15wt%, PDA vesica and concentration are that four kinds of telltales of F68 blend when 5min (40 ℃ the time can variable color) and the vaccine of 15wt% puts together, 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 determine optionally so so whether vaccine can continue use and still lose efficacy.
Again such as, meet accident in storage or the transportation, raise suddenly such as 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, illustrate that unusually should not use has 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 using method of above-mentioned time-temperature color-changing indicator, and concrete steps are:
(1) it is for subsequent use to dispose respectively the amphipathic nature polyalcohol aqueous solution and the PDA vesica of desired concn;
(2) with the amphipathic nature polyalcohol aqueous solution and the blend of PDA vesica that configure, blend and article put together;
(3) the 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.
The concentration (wt%) of amphipathic nature polyalcohol during 50 ℃ of lower PDA/ amphipathic nature polyalcohol system variable colors of table 1
Annotate: table 1 variable color refers to that PDA/ amphipathic nature polyalcohol water solution system becomes redness by the visible blueness, and following table together;
"/" in the table 1 in the second row representative: when concentration during less than 0.5wt%, 50 ℃ of lower 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 lower 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 lower 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 lower PDA vesica/Tween-20 mixtures all do not have variable color through 10min, 1h, 3h.
The concentration (wt%) of amphipathic nature polyalcohol during 40 ℃ of lower PDA/ amphipathic nature polyalcohol system variable colors of table 2
Annotate: "/" representative in the table 2 in the second row: when concentration during less than 0.5wt%, 40 ℃ of lower PDA vesica/F127 mixtures do not have variable color through 2h; "/" in the third line representative: when concentration during less than 15wt%, 40 ℃ of lower 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 lower 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 lower PDA vesica/Tween-20 mixtures all do not have variable color through 30min, 1h, 2h.
The concentration (wt%) of amphipathic nature polyalcohol during 30 ℃ of lower PDA/ amphipathic nature polyalcohol system variable colors of table 3
Annotate: "/" representative in the table 3 in the second row: when concentration during less than 10wt%, 30 ℃ of lower 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 lower 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 lower 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 20 ℃ of lower PDA/ amphipathic nature polyalcohol system variable colors of table 4
Annotate: "/" representative in the table 4 in the second row: when concentration during less than 15wt%, 20 ℃ of lower PDA vesica/F127 mixtures do not have variable color through 24h; The respectively representative of "/" in the fifth line: when concentration during less than 40wt%, 20 ℃ of lower PDA vesica/Tween-20 mixtures do not have variable color through 1h; And when concentration during less than 30wt%, 20 ℃ of lower PDA vesica/Tween-20 mixtures pass through 4h does not have variable color.
In addition, being used for 10 ℃ of lower time-temperature indicators of preserving the article that are no more than 2h of monitoring is: PDA vesica and concentration are the Tween-20 blend of 40wt%; Being used for 10 ℃ of lower time-temperature indicators of preserving the article that are no more than 30min of monitoring is: PDA vesica and concentration are the Tween-20 blend of 50wt%.Being used for 0 ℃ of lower time-temperature indicator of preserving the article that are no more than 48h of monitoring is: PDA vesica and concentration are the Tween-20 blend of 50wt%;
Alkynyl one side connection long chain alkane because of the diine monomer, the alkane chain end of opposite side is polar group, so be similar to amphiphilic, the diine monomer can self-assembly in water, formation has double-deck vesica, again through the ultraviolet lighting polymerization, so that original vesica has higher physical strength.Poly-diacetylene (PDA) is a kind of pi-conjugated polymkeric substance, and two keys and triple bond alternately occur generally presenting 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 amphipathic nature polyalcohol has the material of hydrophilic radical and lipophilicity group simultaneously, such as Bai Luoshamu, a kind of PEG-PPG-PEG triblock copolymer, its lipophilicity group can be inserted in the lipid unimolecular layer on above-mentioned PDA vesica surface, along with the variation of temperature or time, be inserted into the lipophilicity group of the APP in the lipid unimolecular layer on above-mentioned vesica surface 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; As seen, the PDA/ amphipathic nature polyalcohol can be used as time-temperature indicator, monitors the Time-temperature change histories in the perishables conveyer chains such as vaccine.
Below form by specific embodiment the present invention is further described, but should not be understood as limitation of the present invention.
1, the Preparation and characterization of PDA vesica
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.Then cooling is 4 ℃ of preservations of spending the night, so that the fat membrane crystallization.Polyreaction was carried out in ice bath 5 minutes under 254nm length ultraviolet rayed.At last, the PDA vesica that obtains be kept at 4 ℃ for subsequent use.By the laser particle analyzer test, the mean particle size of PDA vesica is 128.5 ± 4.8nm.The result is the mean value 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 lower variable colors in lower 1 hour of F127 monitoring
The F127 solution that the PDA vesica for preparing and concentration are 0.5wt% places respectively independent collecting bottle, when article delivery to be monitored, the PDA vesica is divided with the F127 of 0.5wt% mixes, and mixture is put together with needing the transportation article, delivers; When arriving this conveyer chain terminal, change if find certain PDA vesica/F127 mixture color, when namely becoming redness by blueness, illustrate to surpass storing temp, the time of setting, can not eat or use.
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, with mixture with need to transport article and put together, deliver; When arriving this conveyer chain terminal, change if find certain PDA vesica/F127 mixture color, when namely becoming redness by blueness, illustrate to surpass storing temp, the time of setting, can not eat or use.
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 lower 2 days article of 20 degree temperature that PDA/Tween-20 (concentration is 15wt%) is used for the monitoring condition of storage: when article delivery to be monitored, be that 15% Tween-20 mixes with PDA vesica and concentration, mixture is put together with needing the transportation article, delivery, in order to guarantee accuracy, can place simultaneously many group mixtures; When arriving this conveyer chain terminal, change if find certain PDA vesica/Tween-20 mixture color, when namely becoming redness by blueness, illustrate to surpass storing temp, the time of setting, can not eat or use.
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 lower 1 day article of 20 degree temperature that PDA/Tween-20 (concentration is 20wt%) is used for the monitoring condition of storage: when article delivery to be monitored, be that 20% Tween-20 mixes with PDA vesica and concentration, mixture is put together with needing the transportation article, delivery, in order to guarantee accuracy, can place simultaneously many group mixtures; When arriving this conveyer chain terminal, change if find certain PDA vesica/Tween-20 mixture color, when namely becoming redness by blueness, illustrate to surpass storing temp, the time of setting, can not eat or use.
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.
Time-temperature history is not limited to above-described embodiment in the concrete use time-temperature indicator monitoring articles conveyer chain of the present invention, can select flexibly PDA vesica and amphipathic nature polyalcohol according to the Time-temperature change point in the table 1; 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 with 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 monitor in 0～50 ℃ of temperature range change, such as the temperature variation that is used for the monitoring experiment process in the scientific research and time changing conditions etc.
Claims (11)
1. time-temperature color-changing indicator is characterized in that, comprises 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:
M is that 10 ~ 20, n is 3 ~ 10;
Wherein, R is hydrophilic radical, and described hydrophilic radical contains-COOH; R' is hydrophobic grouping, and described hydrophobic grouping contains :-CH
3,
X=1 ~ 10;
Wherein, described amphipathic nature polyalcohol is Bai Luoshamu, Tween-20, Tween-80; The concentration of the described amphipathic nature polyalcohol aqueous solution is 0.001 ~ 50wt%.
2. time-temperature color-changing indicator according to claim 1, it is characterized in that: described diacetylene class material is 10,12-, 23 carbon diacetylenic acids, 2,4-21 carbon diacetylenic acids, 2,4-15 carbon diacetylenic acids or 2,4-, 23 carbon diacetylenic acids.
3. claim 1 or the 2 described time-temperature color-changing indicators temperature variation in 0 ~ 50 ℃ of temperature range of monitoring and/or the application of time variation, it is characterized in that the temperature and/or the time that are used for monitoring in perishable goods transportation process or the storage process change.
4. the temperature variation of time-temperature color-changing indicator claimed in claim 3 in 0 ~ 50 ℃ of temperature range of monitoring and/or the application of time variation, it is characterized in that the temperature and/or the time that are used in monitoring vaccine, biologics transportation or the storage process change.
5. the temperature variation of time-temperature color-changing indicator according to claim 3 in 0 ~ 50 ℃ of temperature range of monitoring and/or the application of time variation is characterized in that:
Being used for 50 ℃ of lower time-temperature indicators of preserving the article that are no more than 5min of monitoring 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 for 50 ℃ of lower time-temperature indicators of preserving the article that are no more than 10min of monitoring is: PDA vesica and concentration are the F127 blend of 0.5wt%; Or
Being used for 40 ℃ of lower time-temperature indicators of preserving the article that are no more than 1h of monitoring is: PDA vesica and concentration are the F127 blend of 0.5wt%; Or
Being used for 40 ℃ of lower time-temperature indicators of preserving the article that are no more than 30min of monitoring is: PDA vesica and concentration are the F127 blend of 2wt%; Or
Being used for 40 ℃ of lower time-temperature indicators of preserving the article that are no more than 5min of monitoring 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 30 ℃ of lower time-temperature indicators of preserving the article that are no more than 4h of monitoring 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 for 30 ℃ of lower time-temperature indicators of preserving the article that are no more than 2h of monitoring is: PDA vesica and concentration are the Tween-20 blend of 15wt%; Or
Being used for 30 ℃ of lower time-temperature indicators of preserving the article that are no more than 1h of monitoring is: PDA vesica and concentration are the Tween-20 blend of 10wt%; Or
Being used for 30 ℃ of lower time-temperature indicators of preserving the article that are no more than 30min of monitoring 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 30 ℃ of lower time-temperature indicators of preserving the article that are no more than 5min of monitoring 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 for 20 ℃ of lower time-temperature indicators of preserving the article that are no more than 48h of monitoring is: PDA vesica and concentration are the Tween-20 blend of 15wt%; Or
Being used for 20 ℃ of lower time-temperature indicators of preserving the article that are no more than 24h of monitoring is: PDA vesica and concentration are the Tween-20 blend of 20wt%; Or
Being used for 20 ℃ of lower time-temperature indicators of preserving the article that are no more than 4h of monitoring is: PDA vesica and concentration are the F127 blend of 15wt%; Or
Being used for 20 ℃ of lower time-temperature indicators of preserving the article that are no more than 2h of monitoring 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 20 ℃ of lower time-temperature indicators of preserving the article that are no more than 30min of monitoring 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 for 20 ℃ of lower time-temperature indicators of preserving the article that are no more than 5min of monitoring is: PDA vesica and concentration are the Tween-20 blend of 50wt%; Or
Being used for 10 ℃ of lower time-temperature indicators of preserving the article that are no more than 4h of monitoring is: PDA vesica and concentration are the Tween-20 blend of 40wt%; Or
Being used for 10 ℃ of lower time-temperature indicators of preserving the article that are no more than 30min of monitoring is: PDA vesica and concentration are the Tween-20 blend of 50wt%; Or
Being used for 0 ℃ of lower time-temperature indicator of preserving the article that are no more than 48h of monitoring is: PDA vesica and concentration are the Tween-20 blend of 50wt%;
Wherein, the molecular structure of 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.
6. the temperature variation of time-temperature color-changing indicator according to claim 4 in 0 ~ 50 ℃ of temperature range of monitoring and/or the application of time variation is characterized in that:
Being used for 50 ℃ of lower time-temperature indicators of preserving the article that are no more than 5min of monitoring 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 for 50 ℃ of lower time-temperature indicators of preserving the article that are no more than 10min of monitoring is: PDA vesica and concentration are the F127 blend of 0.5wt%; Or
Being used for 40 ℃ of lower time-temperature indicators of preserving the article that are no more than 1h of monitoring is: PDA vesica and concentration are the F127 blend of 0.5wt%; Or
Being used for 40 ℃ of lower time-temperature indicators of preserving the article that are no more than 30min of monitoring is: PDA vesica and concentration are the F127 blend of 2wt%; Or
Being used for 40 ℃ of lower time-temperature indicators of preserving the article that are no more than 5min of monitoring 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 30 ℃ of lower time-temperature indicators of preserving the article that are no more than 4h of monitoring 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 for 30 ℃ of lower time-temperature indicators of preserving the article that are no more than 2h of monitoring is: PDA vesica and concentration are the Tween-20 blend of 15wt%; Or
Being used for 30 ℃ of lower time-temperature indicators of preserving the article that are no more than 1h of monitoring is: PDA vesica and concentration are the Tween-20 blend of 10wt%; Or
Being used for 30 ℃ of lower time-temperature indicators of preserving the article that are no more than 30min of monitoring 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 30 ℃ of lower time-temperature indicators of preserving the article that are no more than 5min of monitoring 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 for 20 ℃ of lower time-temperature indicators of preserving the article that are no more than 48h of monitoring is: PDA vesica and concentration are the Tween-20 blend of 15wt%; Or
Being used for 20 ℃ of lower time-temperature indicators of preserving the article that are no more than 24h of monitoring is: PDA vesica and concentration are the Tween-20 blend of 20wt%; Or
Being used for 20 ℃ of lower time-temperature indicators of preserving the article that are no more than 4h of monitoring is: PDA vesica and concentration are the F127 blend of 15wt%; Or
Being used for 20 ℃ of lower time-temperature indicators of preserving the article that are no more than 2h of monitoring 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 20 ℃ of lower time-temperature indicators of preserving the article that are no more than 30min of monitoring 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 for 20 ℃ of lower time-temperature indicators of preserving the article that are no more than 5min of monitoring is: PDA vesica and concentration are the Tween-20 blend of 50wt%; Or
Being used for 10 ℃ of lower time-temperature indicators of preserving the article that are no more than 4h of monitoring is: PDA vesica and concentration are the Tween-20 blend of 40wt%; Or
Being used for 10 ℃ of lower time-temperature indicators of preserving the article that are no more than 30min of monitoring is: PDA vesica and concentration are the Tween-20 blend of 50wt%; Or
Being used for 0 ℃ of lower time-temperature indicator of preserving the article that are no more than 48h of monitoring is: PDA vesica and concentration are the Tween-20 blend of 50wt%;
Wherein, the molecular structure of 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.
7. the temperature variation of time-temperature color-changing indicator according to claim 3 in 0 ~ 50 ℃ of temperature range of monitoring and/or the application of time variation is characterized in that:
(1) a, b, four kinds of time-temperature indicators of c, 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) two kinds of time-temperature indicators of e, 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, four kinds of time-temperature indicators of i, 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
Two kinds of time-temperature indicators of n, 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%;
Wherein, the molecular structure of 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.
8. the temperature variation of time-temperature color-changing indicator according to claim 4 in 0 ~ 50 ℃ of temperature range of monitoring and/or the application of time variation is characterized in that:
(1) a, b, four kinds of time-temperature indicators of c, 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) two kinds of time-temperature indicators of e, 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, four kinds of time-temperature indicators of i, 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
Two kinds of time-temperature indicators of n, 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%;
Wherein, the molecular structure of 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.
9. time-temperature color-changing indicator according to claim 3 is used for temperature variation and/or the time variation in 0 ~ 50 ℃ of temperature range of monitoring, it is characterized in that:
(1) time of article changed in two kinds of time-temperature indicators of A, 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, six kinds of time-temperature indicators of O, 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 two kinds of time-temperature indicators of Q, 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%;
Wherein, the molecular structure of 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.
10. time-temperature color-changing indicator according to claim 4 is used for temperature variation and/or the time variation in 0 ~ 50 ℃ of temperature range of monitoring, it is characterized in that:
(1) time of article changed in two kinds of time-temperature indicators of A, 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, six kinds of time-temperature indicators of O, 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 two kinds of time-temperature indicators of Q, 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%;
Wherein, the molecular structure of 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.
11. the using method of claim 1,2 each described time-temperature color-changing indicators, concrete steps are:
(1) it is for subsequent use to dispose respectively the amphipathic nature polyalcohol aqueous solution and the PDA vesica of desired concn;
(2) with the amphipathic nature polyalcohol aqueous solution and the blend of PDA vesica that configure, blend and article put together;
(3) the 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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| CN201010216478.X | 2010-07-02 | ||
| CN201110167000.7A CN102336996B (en) | 2010-06-22 | 2011-06-21 | Time-temperature color-changing indicator and application and using method thereof |
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| CN102706469B (en) | 2012-06-21 | 2016-08-03 | 黄为民 | Temperature indicating means and temperature indicating labels and the manufacture method of temperature indicating labels |
| CN104267163B (en) * | 2014-09-04 | 2016-04-27 | 江苏省农业科学院 | Shelf life storage indicator, preparation method and the method for inspection |
| 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 |
| 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 |
| 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 |
| CN113532683B (en) * | 2021-07-09 | 2022-06-03 | 江南大学 | Preparation method of time temperature indicator based on polydiacetylene liposome |
| 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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Non-Patent Citations (1)
| Title |
|---|
| Yan-lei Su,et al..effect of amphiphilic molecules upon chromatic transitions of polydiacetylene vesicles in aqueous solutions.《Colloids and Surfaces B: Biointerfaces》.2004,第39卷第113-118页. * |
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