CN106332961B - Application of (1,2, 3-thiadiazole-4-carbonyl) -hexyl carbamate in preparation of fruit preservative - Google Patents

Application of (1,2, 3-thiadiazole-4-carbonyl) -hexyl carbamate in preparation of fruit preservative Download PDF

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CN106332961B
CN106332961B CN201610888219.9A CN201610888219A CN106332961B CN 106332961 B CN106332961 B CN 106332961B CN 201610888219 A CN201610888219 A CN 201610888219A CN 106332961 B CN106332961 B CN 106332961B
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CN106332961A (en
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敬国兴
刘海
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Xiangtan University
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    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23BPRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
    • A23B7/00Preservation or chemical ripening of fruit or vegetables
    • A23B7/14Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10
    • A23B7/153Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of liquids or solids
    • A23B7/154Organic compounds; Microorganisms; Enzymes

Abstract

The invention discloses an application of (1,2, 3-thiadiazole-4-carbonyl) -hexyl carbamate in preparing a fruit preservative, the fruit preservative and a preservation method. By using the fruit preservative disclosed by the invention to treat the litchi fruits according to the preservation method disclosed by the invention, the rotting rate, the browning index and the water loss rate of the litchi fruits can be effectively reduced, and the fruit coloring index, the Vc content, the soluble solid content and the titratable acid in the litchi fruits can not be influenced. The fruit preservative has the advantages of safety, stable property and low price, and the storage and preservation method is simple to operate, can effectively reduce the rotting rate of litchi fruits, prolongs the storage time of litchi, and does not change the flavor of the litchi fruits, thereby improving the economic benefit of the litchi industry.

Description

Application of (1,2, 3-thiadiazole-4-carbonyl) -hexyl carbamate in preparation of fruit preservative
The technical field is as follows:
the invention belongs to the technical field of fruit preservation, and particularly relates to an application of (1,2, 3-thiadiazole-4-carbonyl) -hexyl carbamate in preparation of a fruit preservative, the fruit preservative and a preservation method.
Background art:
litchi (lichi chinensis Sonn.) belonging to Sapindaceae is a typical tropical south subtropical fruit and world-grade famous fruit, wherein Litchi has the largest planting area and the highest total yield in China. However, because of its special shape and structure, litchi is considered one of the least storage-resistant fruits because its peel is very easy to brown and rot, which affects the quality of flesh. The browning mechanism of the picked litchi fruits is complex, and the predecessors have developed various researches mainly including enzymatic browning, dehydration, color and sweet degradation, germ infection and the like.
Azole compounds are highly effective and broad-spectrum antifungal drugs actively researched in recent years, and not only are the azole compounds widely applied to medicines, but also are widely applied to preventing and treating agricultural diseases or used as plant regulators as systemic bactericides in agriculture. The bactericidal activity of azole compounds inhibits the synthesis of ergosterol in vivo by interfering with the activity of cytochrome P-450, and thus are inhibitors of ergosterol biosynthesis. Li (2005) reported novel bacteriostatic agents synthesized from 1,2, 3-thiadiazo-4-carboxylic acid and the like as basic raw materials (1,2, 3-thiadiazo-4-carbonyl) -hexyl carbamate [ carboxylic acid, (1,2, 3-thiadiazol-4-ylcarbonyl) -, hexyl ester; CTE and synthetic pathway are shown in figure 1, and the inhibitor has obvious inhibiting effect on Gibberella zeae and northern leaf blight (Alternaria kikuchiana), but the influence on the germ and quality of the litchi after picking is not reported.
The invention content is as follows:
the first purpose of the invention is to provide the application of (1,2, 3-thiadiazo-4-carbonyl) -hexyl carbamate in preparing fruit preservative.
The fruit preservative is preferably a litchi preservative.
The application takes 1,2, 3-thiadiazo-4-carbonyl-hexyl (1,2, 3-thiadiazo-4-carbonyl) -carbamate [ Carbomic acid, (1,2, 3-thiadiazol-4-ylcarbonyl) -, hexyl ester synthesized by 1,2, 3-thiadiazo-4-carboxylic acid and the like as basic raw materials; CTE (coefficient of thermal expansion) in-vitro inhibition of growth of peronophythora litchi is taken as a research basis, and influences of browning, disease occurrence and quality of litchi fruits subjected to exogenous CTE treatment and litchi fruit inoculated with peronophythora litchi under a room-temperature storage condition are researched. The experimental research shows that the novel bacteriostatic agent CTE can effectively preserve litchi and is expected to become a high-efficiency fruit preservative.
The second purpose of the invention is to provide a fruit preservative which is characterized by containing 2-20 mg/L of (1,2, 3-thiadiazo-4-carbonyl) -hexyl carbamate as an active ingredient. The fruit preservative is preferably a litchi preservative.
The concentration of the (1,2, 3-thiadiazo-4-carbonyl) -hexyl carbamate is preferably 5-10 mg/L.
The third purpose of the invention is to provide a method for storing and preserving the picked litchis, which is characterized by comprising the following steps: selecting litchi fruits which are picked in sunny days, do not have rot, mildew or plant diseases and insect pests, have maturity of eight to nine percent and do not have mechanical damage, putting the litchi fruits into a fruit preservative, soaking for 2-8 min, taking out, airing, bagging, and storing at low temperature or room temperature; the fruit preservative is a solution containing 2-20 mg/L of (1,2, 3-thiadiazole-4-carbonyl) -hexyl carbamate. The bag can be packaged by a polyethylene plastic bag with the thickness of 0.03mm (mainly used for preventing water loss), and the preservation effect of storage at low temperature (storage at 1-4 ℃) is better.
The litchi is preferably Huai Zhi litchi.
Preferably, the fruit preservative is a solution containing 5-10 mg/L of (1,2, 3-thiadiazole-4-carbonyl) -hexyl carbamate.
The invention has the beneficial effects that:
(1) the fruit preservative is a novel preservative: the CTE used in the litchi preservation experiment of the invention has high-efficiency, low-toxicity and broad-spectrum antifungal effect, is a novel preservative with stable property and low price, and can reduce the rotting rate of litchi fruits after being used.
(2) The original characteristics of the fruit are not changed: the fruit preservative used in the invention is not affected by the pH of the food, not only maintains the original color, aroma and taste of the fruit, but also does not cause the loss of nutrient components.
(3) The operation is convenient and flexible: the method for storing and preserving the picked litchis has the advantages of simple operation, short treatment time, low cost and easy popularization and application.
In vitro experiments show that the minimum inhibitory concentration and the minimum bactericidal concentration of CTE to Peronophythora litchi are 5mg/L and 10mg/L respectively. By using the fruit preservative disclosed by the invention to treat the litchi fruits according to the preservation method disclosed by the invention, the rotting rate, the browning index and the water loss rate of the litchi fruits can be effectively reduced, and the fruit coloring index, the Vc content, the soluble solid content and the titratable acid in the litchi fruits can not be influenced. The fruit preservative has the advantages of safety, stable property and low price, and the storage and preservation method is simple to operate, can effectively reduce the rotting rate of litchi fruits, prolongs the storage time of litchi, and does not change the flavor of the litchi fruits, thereby improving the economic benefit of the litchi industry.
Description of the drawings:
FIG. 1 is a scheme showing the synthesis of (1,2, 3-thiadiazo-4-carbonyl) -carbamic acid hexyl ester.
The specific implementation mode is as follows:
the following examples are further illustrative of the present invention and are not intended to be limiting thereof.
Example 1:
the CTE Inhibitory effect of [ (1,2, 3-thiadiazo-4-carbonyl) -hexyl carbamate ] on the growth of Peronophythora litchi (Peronophythora litchii) inhibition in vitro was determined (Table 1), and the Minimum Inhibitory Concentration (MIC) and the Minimum bactericidal Concentration (MFC) of CTE on Peronophythora litchi were determined to be 5mg/L and 10mg/L by the assay test, so the CTE treatment concentrations used in the present experiment were 5mg/L and 10 mg/L.
TABLE 1 Effect of CTE on the growth of P.litchi mycelia
Figure GDA0002213275480000041
Note: "a-d" indicates significant differences between different concentrations at the same time (P <0.05)
Example 2:
a method for storing and keeping litchi fresh after picking by using CTE comprises the following detailed steps:
(1) preparation of experimental materials: the litchi orchard in the Zhanjiang area in Guangdong is picked in the afternoon of sunny days, fresh and clean litchi fruits are selected, the litchi fruits are not rotten, mildewed, damaged by diseases and insects, have no obvious mechanical damage and have the maturity of 8 degrees (most of red peels, part of yellow cracks and ditches and white or reddish endocarps), and the surfaces of the litchi fruits are cleaned by tap water after the litchi fruits are placed overnight.
(2) Preparing a fruit preservative and performing preservation treatment: preparing CTE solutions with the concentration of 5mg/L and 10mg/L (the CTE solutions of 5mg/L and 10mg/L are respectively 5mg and 10mg of CTE are dissolved in a proper amount of water, then water is added to the CTE solution to be constant volume of 1L, and the CTE solutions of 5mg/L and 10mg/L are obtained after uniform mixing); the fruits were divided into three groups for treatment, 360 fruits per group, and the control group, MIC treatment group and MFC treatment group were soaked in water, 5mg/L CTE solution and 10mg/LCTE solution for 3min, respectively. After the treatment, the fruits were taken out and dried, and the fruits were bagged with polyethylene plastic bags with a thickness of 0.03mm, 30 fruits/bag, and stored at 25 ℃.
(3) Samples were taken every 2 days for assay storage period of 6 days. Weighing the initial weight of each group of litchi fruits, repeatedly sampling for three times each time, wherein the statistical indexes are as follows: current quality, number of rottings, browning index, colour, anthocyanin, VC (mg/100g), soluble solids and titratable acid content of each group of fruits.
(4) During storage, the CTE treatment affected each indicator of the litchi fruit as follows:
1) effect of CTE treatment on disease index, browning index, and water loss rate of litchi fruits
In the fruits without phytophthora efflorens, the disease index was lower in the control group fruits stored 2d after harvest (6.27%, table 2), but then gradually increased until the end of storage, the disease spread almost over the whole fruits. The CTE treatment can obviously reduce the increase of the rotting rate of the litchi fruits, the rotting rate of the fruits of the MFC treatment group at the 2d is obviously lower than that of the fruits of the control group (P <0.05), and the rotting rates of the fruits of the MIC and MFC treatment groups at the 4d are 38.43% and 33.33% respectively and are both obviously lower than that of the fruits of the control group (P <0.05) (75.06%).
TABLE 2 Effect of CTE treatment on postharvest litchi decay Rate
Figure GDA0002213275480000051
Note: "a-c" indicates significant differences between treatments at the same time (P <0.05)
As can be seen from table 3, the control group of litchi fruits which were not inoculated with phytophthora parasitica showed a slight browning degree (browning index <1) within 2d of storage, but then the browning index rapidly increased; almost all of the control fruits were browned by 6 d. The CTE treatment delays the increase of the browning index of the litchi fruits in the storage period, and the browning indexes of the fruits in the treated groups are all obviously lower than those in the control group (P < 0.05).
TABLE 3 Effect of CTE treatment on post-harvest litchi browning Rate
Figure GDA0002213275480000052
Figure GDA0002213275480000061
Note: "a-c" indicates significant differences between treatments at the same time (P <0.05)
The water loss rate of the fruits in the storage period is in an increasing trend (table 4), the CTE treatment delays the increase of the water loss rate of the litchi fruits, the water loss rates of the MIC treatment group and the MFC treatment group at the 6d are respectively 1.63 percent and 1.56 percent, and are both obviously lower than the water loss rate of the litchi fruits in a control group (P is less than 0.05 and 2.16 percent).
TABLE 4 Effect of CTE treatment on postharvest litchi Water loss
Figure GDA0002213275480000062
Note: "a-c" indicates significant differences between treatments at the same time (P <0.05)
2) Effect of CTE treatment on litchi pericarp color
As can be seen from table 5, the peel a value of the litchi of the control group not inoculated with peronophythora frigida showed a trend of increasing first and then decreasing, the peel a value reached a maximum at 2d of the storage period, the peel a value of the control group was 22.0, which was significantly higher than that of the MFC treated group (20.83, P <0.05), and then the peel a value of the control group decreased and was significantly lower than that of the MFC treated group (P < 0.05).
TABLE 5 Effect of CTE treatment on post-harvest litchi chroma (a)
Figure GDA0002213275480000063
Figure GDA0002213275480000071
Note: "a-c" indicates significant differences between treatments at the same time (P <0.05)
3) Effect of CTE treatment on anthocyanin content of litchi pericarp
As can be seen from Table 6, the anthocyanin content of litchi peels which are not inoculated with peronophythora rosea shows a trend of increasing first and then decreasing, until the anthocyanin content of the litchi peels reaches the maximum value at the 2 nd day, the anthocyanin content of the litchi peels in the control group is 0.17mg g-1FW, significantly higher than at MFCReason group (P)<0.05), followed by a sharp decrease in control anthocyanin level, whereas the treated group was relatively quantitatively stable with a significantly higher pericarp anthocyanin level at day 4 than the control (P)<0.05)。
TABLE 6 Effect of CTE treatment on post-harvest litchi anthocyanin content
Figure GDA0002213275480000072
Note: "a-c" indicates significant differences between treatments at the same time (P <0.05)
4) Effect of CTE treatment on Vc, TA and TSS of litchi fruits
As can be seen from Table 7, the Vc content in the litchi pulp all showed a decreasing trend. The Vc content in CTE-treated fruits not inoculated with peronospora parasitica during storage was consistently significantly higher than the control group (P <0.05), but there was no significant difference in Vc content between MIC and MFC-treated groups.
TABLE 7 Effect of CTE treatment on post-harvest litchi Vc content
Note: "a-c" indicates significant differences between treatments at the same time (P <0.05)
Overall, TA levels in litchi pulp all showed a decreasing trend (table 8). At shelf life 2d, TA levels in CTE-treated fruits not inoculated with peronospora parasitica were significantly higher than in the control group (P <0.05), but the TA levels in the 2d post-treated and control groups were not significantly different.
TABLE 8 Effect of CTE treatment on TA content of post-harvest litchi
Figure GDA0002213275480000082
Note: "a-c" indicates significant differences between treatments at the same time (P <0.05)
From table 9, it can be seen that the TSS content in the litchi pulp not inoculated with peronophythora scoparia during storage is in a trend of increasing first and then decreasing, the TSS content reaches the maximum value at the 2 nd day of storage, and the TSS content of the control group is 15.13%, which is significantly higher than that of the treatment group.
TABLE 9 Effect of CTE treatment on TSS content of post-harvest litchi
Figure GDA0002213275480000083
Figure GDA0002213275480000091
Note: "a-c" indicates significant differences between treatments at the same time (P <0.05)
Example 3:
a method for storing and keeping litchi fresh after harvesting by using CTE is different from the method in example 2 only in that a control group, an MIC treatment group and an MFC treatment group are soaked in water, a 5mg/L CTE solution and a 10mg/L CTE solution for 2min respectively.
The results show that the CTE treatment of the picked litchi fruits can effectively reduce the fruit rot rate, the browning index and the water loss rate, and the fruit coloring index, the Vc content, the soluble solid content and the titratable acid in the fruits are not influenced.
Example 4:
a method for storing and keeping litchi fresh after harvesting by using CTE is different from the method in the example 2 only in that a control group, an MIC treatment group and an MFC treatment group are soaked in water, a 5mg/L CTE solution and a 10mg/L CTE solution for 8min respectively.
The results show that the CTE treatment of the picked litchi fruits can effectively reduce the fruit rot rate, the browning index and the water loss rate, and the fruit coloring index, the Vc content, the soluble solid content and the titratable acid in the fruits are not influenced.
Example 5:
a method for storing and keeping litchi fresh after picking by using CTE comprises the following detailed steps:
(1) preparation of experimental materials: the litchi orchard in the Zhanjiang area in Guangdong is picked in the afternoon of sunny days, fresh and clean litchi fruits are selected, the litchi fruits are not rotten, mildewed, damaged by diseases and insects, have no obvious mechanical damage and have the maturity of 8 degrees (most of red peels, part of yellow cracks and ditches and white or reddish endocarps), and the surfaces of the litchi fruits are cleaned by tap water after the litchi fruits are placed overnight.
(2) Preparing a fruit preservative and performing preservation treatment: preparing CTE solutions with the concentration of 5mg/L and 10mg/L (the CTE solutions of 5mg/L and 10mg/L are respectively 5mg and 10mg of CTE are dissolved in a proper amount of water, then water is added to the CTE solution to be constant volume of 1L, and the CTE solutions of 5mg/L and 10mg/L are obtained after uniform mixing); the fruits were divided into three groups for treatment, 360 fruits per group, and the fruits of the control group, MIC-treated group and MFC-treated group were soaked in water, 5mg/L CTE solution and 10mg/L CTE solution for 3min, respectively. And taking out and airing after the treatment is finished.
(3) And (3) fungus culture: the Peronophythora litchi strain used in the experiment was inoculated on PDA medium, cultured at 28 ℃ for 4 days, and then the fungal hyphae were eluted with 250mL of sterile water containing 0.02% Tween 20 by volume fraction. Oscillating the hypha suspension for 3h, and filtering with two layers of gauze to obtain filtrate, namely the spore suspension; the final concentration of the prepared spore suspension was 1X 10 as determined by a hemosphere counter6spores/mL.
(4) Inoculation and storage: the fruits which are subjected to fresh-keeping treatment by water, 5mg/L CTE solution and 10mg/L CTE solution are used for being inoculated with peronophythora litchi. 4 wounds of 0.05mm (depth) × 1mm (width) were cut on the equator of the fruit with the inoculating needle sterilized by alcohol flame. Soaking fruits in spore suspension for 2min, and air drying. All fruits (fruits inoculated with and not inoculated with peronophythora frost) were packed in small plastic lunch boxes (6 fruits/box) and covered with 0.03mm thick polyethylene plastic bags to maintain a relative humidity of about 95%, and stored at 25 ℃.
(5) Samples were taken every 2 days for assay storage period of 6 days. Weighing the initial weight of each group of litchi fruits, repeatedly sampling for three times each time, wherein the statistical indexes are as follows: current quality, number of rottings, browning index, colour, anthocyanin, VC (mg/100g), soluble solids and titratable acid content of each group of fruits.
(6) During storage, the CTE treatment affected each indicator of the litchi fruits inoculated with Peronophythora litchi (Peronophythora litchi) as follows:
1) effect of CTE treatment on disease index, browning index, and water loss rate of litchi fruits
The rotting rate of fruits inoculated with the phytophthora parasitica is obviously accelerated (Table 10), but the CTE treatment can delay the infection of the phytophthora parasitica on litchi fruits, the rotting rates of MIC and MFC treatment groups at 4d are 77.78% and 75.56%, respectively, and are significantly lower than (P <0.05) the rotting rate of the fruits of a control group (95.56%), but the fruits of the control group and the treated group are rotten seriously at 6d, and the commercial value is lost.
TABLE 10 Effect of CTE treatment on postharvest litchi decay Rate
Figure GDA0002213275480000111
Note: "a-c" indicates a significant difference between treatments at the same time (P <0.05)
The browning index of the fruits inoculated with the peronophythora bacteria is increased rapidly in the storage period (table 11), and by the time of the 2d storage period, the browning index of the fruits inoculated with the peronophythora bacteria in the control group is over 2 and is obviously higher than that of the fruits inoculated with the peronophythora bacteria in the control group (P < 0.05). The browning speed of the fruit after CTE treatment is relatively inhibited, the browning indexes of the fruit at 2d are all obviously lower than that of a control group (P <0.05), the browning indexes rapidly rise after 2d (the browning indexes are greater than 2), and the browning indexes of the MFC treatment group are still obviously lower than that of the control group at 4 d.
TABLE 11 Effect of CTE treatment on postharvest litchi decay Rate
Figure GDA0002213275480000112
Note: "a-c" indicates a significant difference between treatments at the same time (P <0.05)
The water loss rate of the fruits inoculated with the peronophythora antifrost fungus increases rapidly in the whole storage period (table 12), and the water loss rate of the fruits of the control group inoculated with the peronophythora antifrost fungus already exceeds 1% when the fruits are stored at the 2 nd day, is similar to the level of the fruits of the 4 th day of the control group without the peronophythora antifrost fungus, is obviously higher than that of the CTE (P <0.05), but the water loss rate of the fruits of the control group and the treatment group is not obviously different until the 6 th day.
TABLE 12 Effect of CTE treatment on postharvest litchi Water loss
Figure GDA0002213275480000121
Note: "a-c" indicates a significant difference between treatments at the same time (P <0.05)
2) Effect of CTE treatment on litchi pericarp color
The pericarp a values of the peronospora parasitica inoculated fruits tended to decrease throughout the storage period (table 13), and the pericarp a values of the control group were significantly lower than those of the treatment group (P < 0.05).
TABLE 13 Effect of CTE treatment on post-harvest litchi chroma (a)
Figure GDA0002213275480000122
Note: "a-c" indicates a significant difference between treatments at the same time (P <0.05)
3) Effect of CTE treatment on anthocyanin content of litchi pericarp
The pericarp anthocyanin content of the peronospora parasitica inoculated fruit showed a decreasing trend throughout the storage period (table 14), and the pericarp anthocyanin content of the control group was significantly lower than that of the treated group at 2d and 6d (P < 0.05).
TABLE 14 Effect of CTE treatment on post-harvest anthocyanin content
Figure GDA0002213275480000131
Note: "a-c" indicates a significant difference between treatments at the same time (P <0.05)
4) Effect of CTE treatment on Vc, TA and TSS of litchi fruits
Within 4 days before the storage period, the Vc content of the litchi fruits inoculated with the CTE of the peronophythora is obviously higher than that of the litchi fruits of the control group (P <0.05), but the Vc content of the litchi fruits of the control group and the treatment group at the 6 th day is not obviously different (Table 15).
TABLE 15 Effect of CTE treatment on postharvest Vc content
Figure GDA0002213275480000132
Note: "a-c" indicates a significant difference between treatments at the same time (P <0.05)
The TA content in the fruits inoculated with the phytophthora parasitica decreased faster (table 16), the CTE treated fruits were significantly higher than the control group at 2d (P <0.05), the TA content in the MIC treated group was significantly lower than the control group at 4d, and the TA content difference between the fruits of the treated group and the control group was not significant at 6 d.
TABLE 16 Effect of CTE treatment on post-harvest TA content
Figure GDA0002213275480000133
Figure GDA0002213275480000141
Note: "a-c" indicates a significant difference between treatments at the same time (P <0.05)
The fruit inoculated with p.frostbite showed a decrease in pulp TSS content throughout the storage period (table 17), but overall, the pulp TSS content was higher in the whole storage period treated group than in the control group (P < 0.05).
TABLE 17 Effect of CTE treatment on TSS content post-harvest
Figure GDA0002213275480000142
Note: "a-c" indicates a significant difference between treatments at the same time (P <0.05)
In conclusion, the storage and preservation method disclosed by the invention is very simple to operate, and the CTE treatment of the picked litchi fruits can effectively reduce the fruit rot rate, browning index and water loss rate without influencing the fruit coloring index, Vc content, soluble solid content and titratable acid in the fruits.

Claims (4)

  1. Application of (1,2, 3-thiadiazo-4-carbonyl) -hexyl carbamate in preparation of litchi preservative.
  2. 2. The method for storing and preserving the picked litchis is characterized by comprising the following steps of: selecting litchi fruits which are picked in sunny days, do not have rot, mildew or plant diseases and insect pests, have maturity of eight to nine percent and do not have mechanical damage, putting the litchi fruits into a fruit preservative, soaking for 2-8 min, taking out, airing, bagging, and storing at low temperature or room temperature;
    the fruit preservative is a solution containing 2-20 mg/L (1,2, 3-thiadiazole-4-carbonyl) -hexyl carbamate;
    the low temperature is 1-4 ℃.
  3. 3. The method for storing and refreshing the picked litchis according to claim 2, wherein the litchis are Huai Zhi litchi.
  4. 4. The method for storing and refreshing the picked litchis according to claim 2 or 3, wherein the fruit preservative is a solution containing 5-10 mg/L of (1,2, 3-thiadiazo-4-carbonyl) -hexyl carbamate.
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Title
Synthesis and Antifungal Activities of Alkyl N-(1,2,3-Thiadiazole-4-Carbonyl) Carbamates and S-Alkyl N-(1,2,3-Thiadiazole-4-Carbonyl) Carbamothioates;Zaifeng Li等;《J. Agric. Food Chem.》;20050421;第53卷;第3872-3876页 *

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