脱落酸光降解机理、稳定方法及其生理效应评价
发布时间：2018-07-31 06:44
【摘要】：脱落酸(abscisic acid, ABA)是重要的植物激素,调节着植物生长,信号转导以及植物免疫防御等。外源施用ABA具有延长花期、增加果实着色率及提高作物抗旱能力等多种功效。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的光降解和光稳定方法研究报道较少。本研究建立了ABA光降解动力学方程,并根据方程研究了不同环境因素对ABA光降解影响,还利用HPLC-MS/MS分析了ABA的衰减产物,进一步明确了ABA的光降解机理；根据ABA的光降解机理研究了不同光保护剂对减少ABA光降解的效果,合成了ABA与己酸二乙氨基乙醇酯配合物。本研究为阐释ABA光降解机理、研制光稳定产品以及生产应用提供理论指导。主要结果如下：1.在紫外辐照下,ABA遵从先有近似50%异构化为trans-ABA,再与生成的trans-ABA一起衰减的规律,异构化和衰减分别符合一级对峙反应和一级反应特征方程。在pH为8的缓冲体系中,ABA异构化速率常数为0.0466 min-1,平衡时间为55 mmin,进一步衰减半衰期为506min,分别比在pH为3时小94%以及增加41倍和近40倍。ABA浓度为280 mg/l时,其异构化速率常数为0.0182min-1,平衡时间为58min,进一步衰减半衰期为521min,分别比5mg/l时小96%,增加近17倍和10倍。ABA光异构化速率常数在10℃时与其在22℃时没有明显差异,在40℃时其速率常数略有下降,且差异显著。将氙光灯中的紫外滤去后,ABA在可见光下照射40.7小时后剩余98%,而未滤紫外对照中ABA已经几乎降解完毕。ABA在高压汞灯下的光异构化速率常数比在氙光灯下快4.5倍,平衡时间加快76%,进一步衰减半衰期加快62%,这可能是汞灯紫外强度高于后者20倍所致。因此,可得出以下结论：可见光不影响ABA的光降解；紫外光是促成ABA降解的主因且与强度成正相关；阴离子形式的ABA有助于减缓其降解；pH及紫外辐照强度一定时,高浓度ABA降解较慢；在10-40℃范围内温度升高不会加快ABA的光降解。2.根据液相色谱图及质谱总离子流图,发现了ABA衰减时期的4个主产物。利用各组分的紫外全扫图谱及一级二级质谱并结合trans-ABA、ABA标准品图谱对各组分结构进行了解析,发现ABA在衰减时期除生成的trans-ABA外,主要生成了4-trans-3-methylene ABA、 4-cis-3-methylene ABA等ABA同分异构体。因此,结合结果1可推断ABA的光降解机理为：在紫外照射下,ABA先异构化为trans-ABA,再衰减为4-trans-3-methylene ABA、4-cis-3-methyleneABA等产物,期间ABA浓度和pH值的降低、紫外强度的加强都会加快ABA降解。3.水溶性紫外吸收剂2-羟基4-甲氧基-5-磺酸二苯甲酮(BP-4)和油溶性紫外吸收剂2-羟基-4-正辛氧基二苯甲酮(UV-531)显著减少了ABA的光降解,且二者没有显著差异。光稳定剂双(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,且未加强BP-4作用效果。添加有200 mg/1 BP-4的280mg/1ABA经紫外照射2小时后,ABA剩余比仅含ABA对照多26 %,该溶液的300倍稀释液对小麦种子(济麦22)芽及根伸长的抑制活性比仅含ABA的对照稀释液高13%以上。因此,可以得出结论,水溶性紫外吸收剂BP-4是一种能够显著提高ABA在紫外下稳定性的高效添加剂。4.添加有2000 mg/1木质素磺酸盐Ufoxane 3A的280 mg/1 ABA经紫外照射2小时后,ABA剩余为92%,而仅含ABA对照剩余40%,该溶液的300倍稀释液对小麦芽及根伸长的抑制活性比仅含ABA的对照稀释液高近20%。其它种类木质素磺酸盐对ABA光稳定效果与Ufoxane 3A相比无显著差异。Ufoxane 3A在2000 mg/1及以下浓度时,与清水对照相比,对小麦种子发芽及生长并无胁迫效应以及生物活性。因此,可以得出结论,木质素磺酸盐是一类能够显著提高ABA在紫外下稳定性的添加剂。而且由于无毒无害,能生物降解,它们能够维持在较高的添加剂量以达到最优效果。5.合成的ABA与己酸二乙氨基乙醇酯配合物经核磁确证且配合比为1/1。配合物在紫外光下的稳定性显著高于pH为6及以下缓冲体系中的ABA,对小麦种子萌发的抑制活性比ABA高13%,表现出较好的植物生长调节活性。
[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.
【学位授予单位】：中国农业大学
【学位级别】：博士
【学位授予年份】：2016
【分类号】：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.
【学位授予单位】：中国农业大学
【学位级别】：博士
【学位授予年份】：2016
【分类号】：Q945
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