脫落酸光降解機(jī)理、穩(wěn)定方法及其生理效應(yīng)評價(jià)
發(fā)布時(shí)間：2018-07-31 06:44
【摘要】：脫落酸(abscisic acid, ABA)是重要的植物激素,調(diào)節(jié)著植物生長,信號轉(zhuǎn)導(dǎo)以及植物免疫防御等。外源施用ABA具有延長花期、增加果實(shí)著色率及提高作物抗旱能力等多種功效。然而,在光照下ABA很容易降解失活,大大降低了其使用效果。而且,ABA的光降解和光穩(wěn)定方法研究報(bào)道較少。本研究建立了ABA光降解動(dòng)力學(xué)方程,并根據(jù)方程研究了不同環(huán)境因素對ABA光降解影響,還利用HPLC-MS/MS分析了ABA的衰減產(chǎn)物,進(jìn)一步明確了ABA的光降解機(jī)理；根據(jù)ABA的光降解機(jī)理研究了不同光保護(hù)劑對減少ABA光降解的效果,合成了ABA與己酸二乙氨基乙醇酯配合物。本研究為闡釋ABA光降解機(jī)理、研制光穩(wěn)定產(chǎn)品以及生產(chǎn)應(yīng)用提供理論指導(dǎo)。主要結(jié)果如下：1.在紫外輻照下,ABA遵從先有近似50%異構(gòu)化為trans-ABA,再與生成的trans-ABA一起衰減的規(guī)律,異構(gòu)化和衰減分別符合一級對峙反應(yīng)和一級反應(yīng)特征方程。在pH為8的緩沖體系中,ABA異構(gòu)化速率常數(shù)為0.0466 min-1,平衡時(shí)間為55 mmin,進(jìn)一步衰減半衰期為506min,分別比在pH為3時(shí)小94%以及增加41倍和近40倍。ABA濃度為280 mg/l時(shí),其異構(gòu)化速率常數(shù)為0.0182min-1,平衡時(shí)間為58min,進(jìn)一步衰減半衰期為521min,分別比5mg/l時(shí)小96%,增加近17倍和10倍。ABA光異構(gòu)化速率常數(shù)在10℃時(shí)與其在22℃時(shí)沒有明顯差異,在40℃時(shí)其速率常數(shù)略有下降,且差異顯著。將氙光燈中的紫外濾去后,ABA在可見光下照射40.7小時(shí)后剩余98%,而未濾紫外對照中ABA已經(jīng)幾乎降解完畢。ABA在高壓汞燈下的光異構(gòu)化速率常數(shù)比在氙光燈下快4.5倍,平衡時(shí)間加快76%,進(jìn)一步衰減半衰期加快62%,這可能是汞燈紫外強(qiáng)度高于后者20倍所致。因此,可得出以下結(jié)論：可見光不影響ABA的光降解；紫外光是促成ABA降解的主因且與強(qiáng)度成正相關(guān)；陰離子形式的ABA有助于減緩其降解；pH及紫外輻照強(qiáng)度一定時(shí),高濃度ABA降解較慢；在10-40℃范圍內(nèi)溫度升高不會(huì)加快ABA的光降解。2.根據(jù)液相色譜圖及質(zhì)譜總離子流圖,發(fā)現(xiàn)了ABA衰減時(shí)期的4個(gè)主產(chǎn)物。利用各組分的紫外全掃圖譜及一級二級質(zhì)譜并結(jié)合trans-ABA、ABA標(biāo)準(zhǔn)品圖譜對各組分結(jié)構(gòu)進(jìn)行了解析,發(fā)現(xiàn)ABA在衰減時(shí)期除生成的trans-ABA外,主要生成了4-trans-3-methylene ABA、 4-cis-3-methylene ABA等ABA同分異構(gòu)體。因此,結(jié)合結(jié)果1可推斷ABA的光降解機(jī)理為：在紫外照射下,ABA先異構(gòu)化為trans-ABA,再衰減為4-trans-3-methylene ABA、4-cis-3-methyleneABA等產(chǎn)物,期間ABA濃度和pH值的降低、紫外強(qiáng)度的加強(qiáng)都會(huì)加快ABA降解。3.水溶性紫外吸收劑2-羥基4-甲氧基-5-磺酸二苯甲酮(BP-4)和油溶性紫外吸收劑2-羥基-4-正辛氧基二苯甲酮(UV-531)顯著減少了ABA的光降解,且二者沒有顯著差異。光穩(wěn)定劑雙(2,2,6,6-四甲基-4-哌啶基)癸二酸酯(HS-770)加速了ABA的光降解,且未加強(qiáng)BP-4作用效果。添加有200 mg/1 BP-4的280mg/1ABA經(jīng)紫外照射2小時(shí)后,ABA剩余比僅含ABA對照多26 %,該溶液的300倍稀釋液對小麥種子(濟(jì)麥22)芽及根伸長的抑制活性比僅含ABA的對照稀釋液高13%以上。因此,可以得出結(jié)論,水溶性紫外吸收劑BP-4是一種能夠顯著提高ABA在紫外下穩(wěn)定性的高效添加劑。4.添加有2000 mg/1木質(zhì)素磺酸鹽Ufoxane 3A的280 mg/1 ABA經(jīng)紫外照射2小時(shí)后,ABA剩余為92%,而僅含ABA對照剩余40%,該溶液的300倍稀釋液對小麥芽及根伸長的抑制活性比僅含ABA的對照稀釋液高近20%。其它種類木質(zhì)素磺酸鹽對ABA光穩(wěn)定效果與Ufoxane 3A相比無顯著差異。Ufoxane 3A在2000 mg/1及以下濃度時(shí),與清水對照相比,對小麥種子發(fā)芽及生長并無脅迫效應(yīng)以及生物活性。因此,可以得出結(jié)論,木質(zhì)素磺酸鹽是一類能夠顯著提高ABA在紫外下穩(wěn)定性的添加劑。而且由于無毒無害,能生物降解,它們能夠維持在較高的添加劑量以達(dá)到最優(yōu)效果。5.合成的ABA與己酸二乙氨基乙醇酯配合物經(jīng)核磁確證且配合比為1/1。配合物在紫外光下的穩(wěn)定性顯著高于pH為6及以下緩沖體系中的ABA,對小麥種子萌發(fā)的抑制活性比ABA高13%,表現(xiàn)出較好的植物生長調(diào)節(jié)活性。
[Abstract]:Abscisic acid (ABA) is an important plant hormone that regulates plant growth, signal transduction and plant immune defense. Exogenous application of ABA has many functions such as prolonging florescence, increasing fruit coloring rate and improving crop drought resistance. However, under light, ABA can easily degrade deactivation and greatly reduce its use effect. Moreover, ABA There are few reports on photodegradation and photostabilization methods. This study established the kinetic equation of ABA photodegradation, and studied the effect of different environmental factors on the degradation of ABA photodegradation according to the equation. The degradation products of ABA were analyzed by HPLC-MS/MS, and the photodegradation mechanism of ABA was further clarified. The photodegradation mechanism of ABA was studied according to the photodegradation mechanism of ABA. In order to reduce the effect of ABA photodegradation, the combination of ABA and hexanoate two ethanolates was synthesized. This study provides theoretical guidance for explaining the mechanism of ABA photodegradation, developing photostable products and production applications. The main results are as follows: 1. under ultraviolet radiation, ABA follows an approximate 50% isomerization to trans-ABA, and then with the generated trans-ABA In the buffer system with pH 8, the rate constant of ABA isomerization is 0.0466 min-1, the equilibrium time is 55 mmin, and the further attenuating half-life is 506min, 94% and 41 times and 40 times the.ABA concentration of 280 mg/l, respectively, when pH is 3, respectively. The rate constant of isomerization is 0.0182min-1, the equilibrium time is 58min, the further attenuating half-life is 521min, which is 96% smaller than that of 5mg/l, and the rate constant of.ABA photoisomerization is nearly 17 times and 10 times higher than that at 10. The rate constant of the isomerization is not obviously different from that at 22. The rate constant of the isomerization is slightly decreased at 40 C, and the difference is significant. After 40.7 hours of visible light irradiation, the residual ABA was 98%, while the ABA in the unpurplish control was nearly degraded by 4.5 times faster than that under the high pressure mercury lamp, 4.5 times faster than that under the xenon light lamp, the balance time accelerated by 76%, and the further attenuating half-life accelerated by 62%, which could be caused by the ultraviolet intensity of the mercury lamp was 20 times higher than that of the latter. It can be concluded that light does not affect the photodegradation of ABA; ultraviolet light is the main cause of the degradation of ABA and is positively related to the strength; the ABA of the anionic form helps to slow down its degradation; the high concentration ABA degradation is slow when the pH and ultraviolet radiation intensity is certain, and the increase of temperature within the range of 10-40 degrees does not accelerate the photodegradation of.2. based on ABA. 4 main products of ABA attenuation period were found by liquid chromatography and mass spectrogram of mass spectrometry. The components of each component were analyzed by UV total sweep and first order two mass spectrometry, combined with trans-ABA, ABA standard atlas. It was found that 4-trans-3-methylene ABA was mainly produced in the decay period, except for the generated trans-ABA, 4. -cis-3-methylene ABA and other ABA isomers. Therefore, combined with the result 1, it can be concluded that the photodegradation mechanism of ABA is: under UV irradiation, ABA isomerization to trans-ABA, then 4-trans-3-methylene ABA, 4-cis-3-methyleneABA and so on, and the decrease of ABA concentration and pH value, and the enhancement of UV intensity will accelerate the solubility of water solubility of ABA. UV Absorbents 2- hydroxyl 4- methoxy -5- sulfonic acid two benzophenone (BP-4) and oil soluble UV Absorbents 2- hydroxyl -4- oxo benzophenone (UV-531) significantly reduced the photodegradation of ABA, and there was no significant difference between the two. The light stabilizer double (2,2,6,6- four methyl -4- piperidine) sebacate (HS-770) accelerated the photodegradation of ABA, and did not strengthen The effect. After 2 hours of UV irradiation with 200 mg/1 BP-4, the residual ratio of ABA was 26% more than that of ABA control. The inhibitory activity of 300 times dilution of the solution on wheat seed (Jimmy 22) bud and root elongation was more than 13% higher than that of a control diluent only containing ABA. Therefore, it was concluded that a water-soluble UV absorber BP-4 is a kind. The high efficiency additive.4. can significantly increase the stability of ABA under UV, 280 mg/1 ABA with 2000 mg/1 lignosulfonate Ufoxane 3A after UV irradiation for 2 hours, and ABA remaining 92%, but only ABA control remaining 40%. The inhibitory activity of the 300 times diluent on the malt and root elongation is nearly 20% higher than that of a control diluent containing ABA only. Other kinds of lignosulfonate have no significant difference in ABA light stabilization effect compared with Ufoxane 3A. When.Ufoxane 3A is at 2000 mg/1 and below the concentration, there is no stress effect and biological activity on the germination and growth of wheat seeds compared with clear water. Therefore, it can be concluded that lignosulfonate can significantly improve ABA in purple. In addition to the additives for the stability of the outside, and because of innocuity and harmlessness, they can be biodegraded and they can be maintained at a high dosage to achieve the optimal effect of.5. synthesis of ABA and hexanoate two ethanolate complex by NMR and the stability of the coordination ratio of 1/1. complex in ultraviolet light is significantly higher than that of pH in the buffer system of 6 and below. ABA inhibited the germination of wheat seeds by 13% higher than that of ABA, and showed better plant growth regulating activity.
【學(xué)位授予單位】：中國農(nóng)業(yè)大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2016
【分類號】：Q945
[Abstract]:Abscisic acid (ABA) is an important plant hormone that regulates plant growth, signal transduction and plant immune defense. Exogenous application of ABA has many functions such as prolonging florescence, increasing fruit coloring rate and improving crop drought resistance. However, under light, ABA can easily degrade deactivation and greatly reduce its use effect. Moreover, ABA There are few reports on photodegradation and photostabilization methods. This study established the kinetic equation of ABA photodegradation, and studied the effect of different environmental factors on the degradation of ABA photodegradation according to the equation. The degradation products of ABA were analyzed by HPLC-MS/MS, and the photodegradation mechanism of ABA was further clarified. The photodegradation mechanism of ABA was studied according to the photodegradation mechanism of ABA. In order to reduce the effect of ABA photodegradation, the combination of ABA and hexanoate two ethanolates was synthesized. This study provides theoretical guidance for explaining the mechanism of ABA photodegradation, developing photostable products and production applications. The main results are as follows: 1. under ultraviolet radiation, ABA follows an approximate 50% isomerization to trans-ABA, and then with the generated trans-ABA In the buffer system with pH 8, the rate constant of ABA isomerization is 0.0466 min-1, the equilibrium time is 55 mmin, and the further attenuating half-life is 506min, 94% and 41 times and 40 times the.ABA concentration of 280 mg/l, respectively, when pH is 3, respectively. The rate constant of isomerization is 0.0182min-1, the equilibrium time is 58min, the further attenuating half-life is 521min, which is 96% smaller than that of 5mg/l, and the rate constant of.ABA photoisomerization is nearly 17 times and 10 times higher than that at 10. The rate constant of the isomerization is not obviously different from that at 22. The rate constant of the isomerization is slightly decreased at 40 C, and the difference is significant. After 40.7 hours of visible light irradiation, the residual ABA was 98%, while the ABA in the unpurplish control was nearly degraded by 4.5 times faster than that under the high pressure mercury lamp, 4.5 times faster than that under the xenon light lamp, the balance time accelerated by 76%, and the further attenuating half-life accelerated by 62%, which could be caused by the ultraviolet intensity of the mercury lamp was 20 times higher than that of the latter. It can be concluded that light does not affect the photodegradation of ABA; ultraviolet light is the main cause of the degradation of ABA and is positively related to the strength; the ABA of the anionic form helps to slow down its degradation; the high concentration ABA degradation is slow when the pH and ultraviolet radiation intensity is certain, and the increase of temperature within the range of 10-40 degrees does not accelerate the photodegradation of.2. based on ABA. 4 main products of ABA attenuation period were found by liquid chromatography and mass spectrogram of mass spectrometry. The components of each component were analyzed by UV total sweep and first order two mass spectrometry, combined with trans-ABA, ABA standard atlas. It was found that 4-trans-3-methylene ABA was mainly produced in the decay period, except for the generated trans-ABA, 4. -cis-3-methylene ABA and other ABA isomers. Therefore, combined with the result 1, it can be concluded that the photodegradation mechanism of ABA is: under UV irradiation, ABA isomerization to trans-ABA, then 4-trans-3-methylene ABA, 4-cis-3-methyleneABA and so on, and the decrease of ABA concentration and pH value, and the enhancement of UV intensity will accelerate the solubility of water solubility of ABA. UV Absorbents 2- hydroxyl 4- methoxy -5- sulfonic acid two benzophenone (BP-4) and oil soluble UV Absorbents 2- hydroxyl -4- oxo benzophenone (UV-531) significantly reduced the photodegradation of ABA, and there was no significant difference between the two. The light stabilizer double (2,2,6,6- four methyl -4- piperidine) sebacate (HS-770) accelerated the photodegradation of ABA, and did not strengthen The effect. After 2 hours of UV irradiation with 200 mg/1 BP-4, the residual ratio of ABA was 26% more than that of ABA control. The inhibitory activity of 300 times dilution of the solution on wheat seed (Jimmy 22) bud and root elongation was more than 13% higher than that of a control diluent only containing ABA. Therefore, it was concluded that a water-soluble UV absorber BP-4 is a kind. The high efficiency additive.4. can significantly increase the stability of ABA under UV, 280 mg/1 ABA with 2000 mg/1 lignosulfonate Ufoxane 3A after UV irradiation for 2 hours, and ABA remaining 92%, but only ABA control remaining 40%. The inhibitory activity of the 300 times diluent on the malt and root elongation is nearly 20% higher than that of a control diluent containing ABA only. Other kinds of lignosulfonate have no significant difference in ABA light stabilization effect compared with Ufoxane 3A. When.Ufoxane 3A is at 2000 mg/1 and below the concentration, there is no stress effect and biological activity on the germination and growth of wheat seeds compared with clear water. Therefore, it can be concluded that lignosulfonate can significantly improve ABA in purple. In addition to the additives for the stability of the outside, and because of innocuity and harmlessness, they can be biodegraded and they can be maintained at a high dosage to achieve the optimal effect of.5. synthesis of ABA and hexanoate two ethanolate complex by NMR and the stability of the coordination ratio of 1/1. complex in ultraviolet light is significantly higher than that of pH in the buffer system of 6 and below. ABA inhibited the germination of wheat seeds by 13% higher than that of ABA, and showed better plant growth regulating activity.
【學(xué)位授予單位】：中國農(nóng)業(yè)大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2016
【分類號】：Q945
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